Dimethyl Sulfide → 2-(Benzyloxy)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-3-(chloromethyl)-6-methylpyridine

HRID 577445ノート

反応式

HRID 577445 の反応式
C1C(=O)N([Cl:8])C(=O)C1.CSC.[CH2:12]([O:19][C:20]1[C:25]([CH2:26]O)=[C:24]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH:23]=[C:22]([CH3:37])[N:21]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C(Cl)Cl>[CH2:12]([O:19][C:20]1[C:25]([CH2:26][Cl:8])=[C:24]([CH2:28][O:29][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[CH:23]=[C:22]([CH3:37])[N:21]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

参加物

5

反応物 3

HCID 1068Dimethyl SulfideHCID 31398ChlorosuccinimideHCID 86723682[2-(Benzyloxy)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-methylpyridin-3-yl]methanol

生成物 1

HCID 867236832-(Benzyloxy)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-3-(chloromethyl)-6-methylpyridine収率 65.4%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-40 °C

実験手順

To a 0° C. solution of NCS (70.2 mg, 0.515 mmol) in DCM (2 mL) was added DMS (34.9 mg, 0.562 mmol). The reaction mixture was cooled to −40° C., then a solution of [2-(benzyloxy)-4-({[tert-butyl(dimethyl)silyl]oxy}methyl)-6-methylpyridin-3-yl]methanol (Cpd J, 175 mg, 0.468 mmol) in DCM (1 mL) was added drop-wise keeping the internal temperature below −30° C. Upon complete addition the reaction mixture was warmed to room temperature and stirred for 3 hours. The reaction mixture was washed with brine, dried with MgSO4, filtered, then concentrated under vacuum. The residue was purified by column chromatography (0-30% EtOAc/heptane) to give the title compound (Cpd K, 120 mg, 65%) as an oil. 1H NMR (400 MHz, chloroform-d) δ 7.50 (d, J=7.3 Hz, 2H), 7.44-7.29 (m, 3H), 6.94 (s, 1H), 5.46 (s, 2H), 4.83 (s, 2H), 4.70 (s, 2H), 2.47 (s, 3H), 0.97 (s, 9H), 0.14 (s, 6H); MS 392 [M+H].

後処理

  1. customthe internal temperature below −30° C
  2. additionUpon complete addition the reaction mixture
  3. temperaturewas warmed to room temperature
  4. washThe reaction mixture was washed with brine
  5. dry with materialdried with MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe residue was purified by column chromatography (0-30% EtOAc/heptane)

出典と根拠

ORDレコード
ord-23611815b5d44d369db3f80e35f11439
出典データセット
uspto-grants-2015_05
特許番号
US09040515B2

反応ノート

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