Hydrochloric Acid → N,N-Diethyl-2-formyl-6-methoxybenzamide

HRID 1968766ノート

反応式

HRID 1968766 の反応式
C([Li])(CC)C.CN(C)CCN(C)C.[CH2:14]([N:16]([CH2:27][CH3:28])[C:17](=[O:26])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[O:24][CH3:25])[CH3:15].CN(C)[CH:31]=[O:32].Cl>C1COCC1>[CH2:27]([N:16]([CH2:14][CH3:15])[C:17](=[O:26])[C:18]1[C:19]([O:24][CH3:25])=[CH:20][CH:21]=[CH:22][C:23]=1[CH:31]=[O:32])[CH3:28]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 346975N,N-diethyl-2-methoxybenzamideHCID 178418400CID 53628100

生成物 1

HCID 12460617N,N-Diethyl-2-formyl-6-methoxybenzamide収率 105.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

Sec-butyl lithium (99.6 ml, 1.3 M in cyclohexane, 129.45 mmol, 1.3 equiv) was added dropwise at −78° C. to a solution of N,N,N′,N′-tetramethyl-ethane-1,2-diamine (15.04 g, 129.45 mmol, 1.3 equiv) in anhydrous THF (400 ml) under an atmosphere of argon. After 30 minutes at −78° C., a solution of N,N-diethyl-2-methoxy-benzamide (20.64 g, 99.58 mmol) in THF (100 ml) was added dropwise over 50 minutes. After 2 hours at −78° C., N,N-dimethylformamide (8.74 g, 119.49 mmol, 1.2 equiv) was added dropwise. 30 minutes after complete addition, TLC analysis indicated complete conversion. 6N aqueous HCl (90 ml) was carefully added at 0° C. After phase separation, the aqueous phase was extracted with EtOAc. The combined organic layers were washed with brine (2×100 ml), dried over Na2SO4, filtered and concentrated in vacuo to yield the title compound (24.71 g, quant.) in adequate purity for direct use in the next transformation. 1H NMR (400 MHz, CDCl3): δ=9.99 (s, 1H), 7.52 (dd, J=6.6/1.0 Hz, 1H), 7.46 (t, 7.6 Hz, 1H), 7.15 (dd, J=8.3/1.2 Hz, 1H), 3.86 (s, 3H), 3.78-3.68 (m, 1H), 3.58-3.49 (m, 1H), 3.10 (q, J=7.1 Hz, 2H), 1.29 (t, J=7.1 Hz, 3H), 1.01 (t, J=7.3 Hz, 3H). MS (ES+): 236 (M+H)+.

後処理

  1. waitAfter 2 hours at −78° C.
  2. addition30 minutes after complete addition, TLC analysis
  3. customAfter phase separation
  4. extractionthe aqueous phase was extracted with EtOAc
  5. washThe combined organic layers were washed with brine (2×100 ml)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-f4b9d95fb24d45eda953c972243c0f5c
出典データセット
uspto-grants-2013_04
特許番号
US08426440B2

反応ノート

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