Morpholine → HCID 57386559、化合物

HRID 420265ノート

反応式

HRID 420265 の反応式
C(OC([C:7]1([CH2:22][C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[C:25]([F:32])[CH:24]=2)[C:12](=[O:13])[CH:11]([NH:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:10][S:9][CH2:8]1)=O)C=C.N1CCOCC1.C([O-])(O)=O.[Na+]>C1COCC1>[C:18]([O:17][C:15](=[O:16])[NH:14][C@@H:11]1[C:12](=[O:13])[C@H:7]([CH2:22][C:23]2[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[C:25]([F:32])[CH:24]=2)[CH2:8][S:9][CH2:10]1)([CH3:21])([CH3:19])[CH3:20]

参加物

5

反応物 3

HCID 8083MorpholineHCID 516892Sodium BicarbonateHCID 666496345-tert-Butoxycarbonylamino-3-(3-fluoro-4-nitro-benzyl)-4-oxo-tetrahydro-thiopyran-3-carboxylic acid allyl ester

生成物 1

HCID 57386559HCID 57386559、化合物

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
25 °C

実験手順

To a degassed solution of 5-tert-butoxycarbonylamino-3-(3-fluoro-4-nitro-benzyl)-4-oxo-tetra-hydro-thiopyran-3-carboxylic acid allyl ester (3.56 g, 7.6 mmol) and morpholine (1.4 mL, 15.2 mmol) in THF (50 mL) was added under argon Pd(PPh3)4 (0.092 g, 0.076 mmol) and the reaction mixture was stirred at 25° C. for 3 h. The reaction mixture was poured onto cold saturated NaHCO3 solution and extracted with EtOAc. Combined extracts were washed with brine, dried over MgSO4 and evaporated. The residue was re-dissolved in THF (10 mL) and kept at 25° C. for 3 h after addition of a catalytic amount of DBU. The title compound was obtained after evaporation and crystallization from diisopropylether as single diastereoisomer: TLC (hexane-EtOAc 1:2) Rf=0.38; HPLC RtA=2.17 min; ESIMS [M+NH4]+=402; 1H NMR (400 MHz, CDCl3): δ 8.0 (dd, 1H), 7.14 (m, 2H), 5.68 (m, 1H), 4.54 (m, 1H), 3.41 (m, 1H), 3.28 (dd, 1H), 3.14 (m, 1H), 2.84 (ddd, 1H), 2.69 (dd, 1H), 2.65 (m, 2H), 1.42 (s, 9H).

後処理

  1. extractionextracted with EtOAc
  2. washCombined extracts were washed with brine
  3. dry with materialdried over MgSO4
  4. customevaporated
  5. dissolutionThe residue was re-dissolved in THF (10 mL)
  6. waitkept at 25° C. for 3 h
  7. additionafter addition of a catalytic amount of DBU

出典と根拠

ORDレコード
ord-acb3784f7b874f808f7a13895c6ec269
出典データセット
uspto-grants-2012_01
特許番号
US08093406B2

反応ノート

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