Red-Al → 1-phenyl-N-{[(3S)-4-(phenylmethyl)-3-morpholinyl]methyl}methanamine

HRID 419386ノート

反応式

HRID 419386 の反応式
O=[C:2]1[N:7]([CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C@@H:6]([C:15]([NH:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=O)[CH2:5][O:4][CH2:3]1.COCCO[AlH2-]OCCOC.[Na+]>C1(C)C=CC=CC=1>[C:19]1([CH2:18][NH:17][CH2:15][C@H:6]2[CH2:5][O:4][CH2:3][CH2:2][N:7]2[CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

参加物

4

反応物 2

HCID 16684438Red-AlHCID 59452664(3R)-5-oxo-N,4-bis(phenylmethyl)-3-morpholinecarboxamide

生成物 1

HCID 594527491-phenyl-N-{[(3S)-4-(phenylmethyl)-3-morpholinyl]methyl}methanamine収率 94.2%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
50 °C

実験手順

(3R)-5-oxo-N,4-bis(phenylmethyl)-3-morpholinecarboxamide (5.09 g, 15.6 mmol) in toluene (50 mL) cooled to 0° C. Red-Al® (35.0 mL, 7 mL per g carboxamide) added via addition funnel. The ice bath was removed after 2 or 3 mL Red-Al® was added. The reaction was heated at 50° C. overnight. The reaction was cooled to 0° C. and quenched slowly with 1N NaOH (50 mL) followed by diethyl ether (50 mL). The organic layer was washed with 1N NaOH (50 mL), the combined aqueous layer was back extracted with toluene (50 mL) and diethyl ether (50 mL) and dried over MgSO4 to provide the title compound of step D (4.35 g, 14.7 mmol, 94%). 1H NMR (400 MHz, DMSO-d6) δ ppm 1.97 (br. s., 1H), 2.06 (ddd, J=12.0, 9.2, 3.4 Hz, 1H), 2.33-2.41 (m, 1H), 2.43-2.48 (m, 1H), 2.54-2.66 (m, 2H), 3.13 (d, J=13.6 Hz, 1H), 3.32-3.39 (m, 1H), 3.42 (dd, J=11.2, 8.2 Hz, 1H), 3.53 (dt, J=11.1, 3.5 Hz, 1H), 3.57-3.62 (m, 2H), 3.70 (dd, J=11.1, 3.0 Hz, 1H), 3.93 (d, J=13.6 Hz, 1H), 7.16-7.27 (m, 10H).

後処理

  1. customThe ice bath was removed after 2 or 3 mL Red-Al®
  2. additionwas added
  3. temperatureThe reaction was cooled to 0° C.
  4. customquenched slowly with 1N NaOH (50 mL)
  5. washThe organic layer was washed with 1N NaOH (50 mL)
  6. extractionthe combined aqueous layer was back extracted with toluene (50 mL) and diethyl ether (50 mL)
  7. dry with materialdried over MgSO4

出典と根拠

ORDレコード
ord-d24251f530e24db4bd5cdb6105ade199
出典データセット
uspto-grants-2012_01
特許番号
US08093239B2

反応ノート

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