Sodium Hydroxide → (-)-(cis)-7-bromo-8-fluoro-1,3,4,14b-tetrahydro-2H-dibenzo[b,f]pyrido[1,2-d][1,4]oxazepin-1-amine

HRID 1668350ノート

反応式

HRID 1668350 の反応式
[OH-].[Na+].OP1(=O)O[C@@H](C2C=CC=CC=2)C(C)(C)CO1.[Br:19][C:20]1[C:39]([F:40])=[CH:38][C:23]2[O:24][C:25]3[CH:37]=[CH:36][CH:35]=[CH:34][C:26]=3[C@H:27]3[C@H:32]([NH2:33])[CH2:31][CH2:30][CH2:29][N:28]3[C:22]=2[CH:21]=1>C(O)C.C(Cl)Cl>[Br:19][C:20]1[C:39]([F:40])=[CH:38][C:23]2[O:24][C:25]3[CH:37]=[CH:36][CH:35]=[CH:34][C:26]=3[C@H:27]3[C@H:32]([NH2:33])[CH2:31][CH2:30][CH2:29][N:28]3[C:22]=2[CH:21]=1

参加物

4

反応物 2

HCID 14798Sodium HydroxideHCID 67359988(-)-(cis)-7-bromo-8-fluoro-1,3,4,14b-tetrahydro-2H-dibenzo[b,f]pyrido[1,2-d][1,4]oxazepin-1-amine (4S)-2-hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinane 2-oxide

生成物 1

HCID 67358773(-)-(cis)-7-bromo-8-fluoro-1,3,4,14b-tetrahydro-2H-dibenzo[b,f]pyrido[1,2-d][1,4]oxazepin-1-amine収率 100%

試薬・触媒・溶媒 1

HCID 21584144Dichloromethane ethanol溶媒

実験手順

1M NaOH (580 ml, 580 mmol) was added to a solution of (−)-(cis)-7-bromo-8-fluoro-1,3,4,14b-tetrahydro-2H-dibenzo[b,f]pyrido[1,2-d][1,4]oxazepin-1-amine (4S)-2-hydroxy-5,5-dimethyl-4-phenyl-1,3,2-dioxaphosphorinane 2-oxide (1:1) (45,42 g 75 mmol) in 1L of ethanol:CH2Cl2 (1:9), and the resulting biphasic mixture was vigorously stirred at ambient temperature for 0.5 h. The aqueous layer was extracted with CH2Cl2 (400 mL) and the combined organic layers were washed with 0.4M NaOH, dried (Na2SO4) and evaporated under reduced pressure to yield the title compound (27.2 g, 100%). 1H-NMR (400 MHz, CDCl3) 1.40-1.51 (m, 1H), 1.69-1.89 (m, 2H), 2.14-2.22 (m, 1H), 3,11-3.29 (m, 1H), 3.38-3.45 (m, 1H), 3.68-3.76 (m, 2H), 6.87-6.90 (d, J=8.0, 1H), 7.03-7.30 (m, 5H). 19F-NMR (400 MHz, CDCl3) −118.27. (m/z)=363+365 (M+H)+. (e.e. =99.9%) (chiralpak AD-H 25*0.46 cm, heptane:ethanol=8:2). (m/z)=363+365 (M+H)+. [α]D20.5=−202° (c=1.0, CHCl3)

後処理

  1. extractionThe aqueous layer was extracted with CH2Cl2 (400 mL)
  2. washthe combined organic layers were washed with 0.4M NaOH
  3. dry with materialdried (Na2SO4)
  4. customevaporated under reduced pressure

出典と根拠

ORDレコード
ord-7e0b51ef564d49b68d2bc8c0c2290af1
出典データセット
uspto-grants-2011_08
特許番号
US07989442B2

反応ノート

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