Benzyl chloroformate → Benzyl 7-hydroxy-5,6,7,8-tetrahydronaphthalen-1-ylcarbamate

HRID 600806ノート

反応式

HRID 600806 の反応式
[CH2:1]([O:8][C:9](Cl)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Si]([O:19][CH:20]1[CH2:29][C:28]2[C:27]([NH2:30])=[CH:26][CH:25]=[CH:24][C:23]=2[CH2:22][CH2:21]1)(C(C)(C)C)(C)C.C(N(C(C)C)CC)(C)C>C(Cl)Cl>[CH2:1]([O:8][C:9](=[O:10])[NH:30][C:27]1[C:28]2[CH2:29][CH:20]([OH:19])[CH2:21][CH2:22][C:23]=2[CH:24]=[CH:25][CH:26]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

5

反応物 3

HCID 10387Benzyl chloroformateHCID 81531DiisopropylethylamineHCID 587341927-{[Tert-butyl(dimethyl)silyl]oxy}-5,6,7,8-tetrahydronaphthalen-1-amine

生成物 1

HCID 66696602Benzyl 7-hydroxy-5,6,7,8-tetrahydronaphthalen-1-ylcarbamate収率 99.5%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

Benzylchloroformate (6.96 g, 40.8 mmol) was added dropwise to a solution of Example 18B (10.3 g, 37.1 mmol,) and diisopropylethylamine (7.20 g, 55.7 mmol) in 120 mL CH2Cl2 at 0° C. The mixture was stirred for 18 hours gradually warming to ambient temperature after which the volatiles were evaporated under reduced pressure. The residue was purified on silica gel eluting with 25% EtOAc/hexanes which yielded the benzyl carbamate as a light brown oil (15.2 g, 36.9 mmol). This product was taken up in 100 mL THF followed by addition of 1.79 g (111 mmol) of triethylamine trihydrofluoride. After 24 hours, the mixture was concentrated under reduced pressure and the residue partitioned between EtOAc and 1N aq. HCl. The separated organic layer was washed with 1N aq. HCl, brine, dried (Na2SO4), and concentrated under reduced pressure. The crude product was triturated with Et2O, and the solid was collected by vacuum filtration and dried under vacuum at 50° C. resulting 8.82 g (80%) of the title compound as a white solid. 1H NMR (DMSO-d6) δ 8.82 (s, 1H), 7.45-7.30 (m, 5H), 7.14 (d, J=7.0 Hz, 1H), 7.05 (t, J=7.0 Hz, 1H), 6.90 (d, J=7.0 Hz, 1H), 5.12 (s, 2H), 4.77 (d, J=3.7 Hz, 1H), 3.87 (m, 1H), 2.86 (m, 2H), 2.72 (m, 1H), 2.43 (m, 1H), 1.84 (m, 1H), 1.58 (m, 1H); MS (ESI+) m/z 298 (M+H)+.

後処理

  1. customwere evaporated under reduced pressure
  2. customThe residue was purified on silica gel eluting with 25% EtOAc/hexanes which

出典と根拠

ORDレコード
ord-79e1223e56a54e959813b0b759799e9b
出典データセット
uspto-grants-2011_03
特許番号
US07902236B2

反応ノート

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