Diisobutylaluminum hydride → HCID 22860091、化合物

HRID 1720437ノート

反応式

HRID 1720437 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]2[S:13][C:12]([C:14]#[C:15][C@H:16]([N:18]([OH:22])[C:19]([NH2:21])=[O:20])[CH3:17])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.CC(C[AlH]CC(C)C)C>C1COCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:8][C:9]2[S:13][C:12](/[CH:14]=[CH:15]/[C@H:16]([N:18]([OH:22])[C:19]([NH2:21])=[O:20])[CH3:17])=[CH:11][CH:10]=2)=[CH:6][CH:7]=1

参加物

4

反応物 2

HCID 14487Diisobutylaluminum hydrideHCID 3086671Atreleuton

生成物 1

HCID 22860091HCID 22860091、化合物収率 20%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of (R)-N-{3-[5-(4-fluorophenylmethyl)thien-2-yl]-1-methyl-2-propynyl}-N-hydroxyurea (0.316g, 1.05 mmol), prepared as in Example 1, step 4, in THF (8 mL) at -70° C. was added DIBAL (5.23 mL, 5.25 mmol). The reaction was slowly allowed to warm to ambient temperature over 17 hours. The reaction was quenched into an aqueous 1M H3PO4 solution and extracted with ethyl acetate. The combined organic layers were washed with aqueous NaHCO3, dried (MgSO4) and evaporated. The residue was purified by chromatography on silica gel (50% ethyl acetate/hexanes/1% acetic acid). The resulting solid was crystallized from hot ethyl acetate/hexanes to yield 0.063 g (20% ) of E-N-[3-(5-(4-Fluorophenylmethyl)-thien-2-yl)-1-(R)-methyl-2-propenyl]-N-hydroxyurea. m.p. 143°-4° C). MS (DCI/NH3) m/e 321 (M+H)+, 338 (M+NH4)+. 1H NMR (DMSO-d6, 300 MHz) δ1.17(d, J=7.2 Hz, 3H), 4.08 (s, 2H), 4.73 (m, 1H), 5.88 (dd, J=6.3, 15.6 Hz, 1H), 6.33 (s, 2H), 6.55 (d, J=15.6 Hz, 1H), 6.77 (d, J=4.2 Hz, 1H), 6.83 (d, J=4.2 Hz, 1H), 7.12 (m, 2H), 7.29 (m, 2H), 9.02 (s, 1H). Anal Calcd for C17H17FN2O2S: C, 59.98; H, 5.35; N, 8.74. Found C, 60.15; H, 5.11; N, 8.75.

後処理

  1. customThe reaction was quenched into an aqueous 1M H3PO4 solution
  2. extractionextracted with ethyl acetate
  3. washThe combined organic layers were washed with aqueous NaHCO3
  4. dry with materialdried (MgSO4)
  5. customevaporated
  6. customThe residue was purified by chromatography on silica gel (50% ethyl acetate/hexanes/1% acetic acid)
  7. customThe resulting solid was crystallized from hot ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-1ec20c48c35943dfb53959b8ca8a902f
出典データセット
uspto-grants-1996_04
特許番号
US05506261

反応ノート

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