Ethyl Acetate → 1-[5-(1,1-Dioxo-1,2,3,6-tetrahydro-1lambda6-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine

HRID 646911ノート

反応式

HRID 646911 の反応式
ClC1C=C(C=CC=1)C(OO)=O.S1[CH2:17][CH:16]=[C:15]([C:18]2[CH:19]=[CH:20][C:21]([N+:31]([O-:33])=[O:32])=[C:22]([N:24]3[CH2:29][CH2:28][CH:27]([CH3:30])[CH2:26][CH2:25]3)[CH:23]=2)[CH2:14][CH2:13]1.[O-:34][S:35]([O-:37])=O.[Na+].[Na+].CCOC(C)=O>C(Cl)Cl.O>[O:34]=[S:35]1(=[O:37])[CH2:13][CH:14]=[C:15]([C:18]2[CH:19]=[CH:20][C:21]([N+:31]([O-:33])=[O:32])=[C:22]([N:24]3[CH2:29][CH2:28][CH:27]([CH3:30])[CH2:26][CH2:25]3)[CH:23]=2)[CH2:16][CH2:17]1

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 24437Sodium SulfiteHCID 70297m-Chloroperbenzoic acidHCID 586385191-[5-(3,6-Dihydro-2H-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine

生成物 1

HCID 586385131-[5-(1,1-Dioxo-1,2,3,6-tetrahydro-1lambda6-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine収率 64%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-78 °C

実験手順

A mixture of 3-chloroperoxybenzoic acid (77 mg, 0.35 mmol, 77%) in 2 mL of DCM was added slowly to a solution of 1-[5-(3,6-dihydro-2H-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine (as prepared in the previous step, 50 mg, 0.16 mmol) in 2 mL of DCM at −78° C. under Ar. The mixture was stirred at −78° C. for 0.5 h, and then Warmed to RT. Treated with 2 mL of 10% Na2SO3 solution, the mixture was stirred vigorously for 5 min. The mixture was treated with 30 mL of EtOAc and 10 mL of H2O. The aqueous layer was separated and the organic layer was washed with saturated aq NaHCO3 solution (10 mL), H2O (10 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (0-2% EtOAc/DCM) gave 35 mg (64%) of the title compound as a yellow oil: 1H-NMR (CDCl3; 400 MHz): δ 7.77 (d, 1H, J=8.6 Hz), 7.00 (d, 1H, J=1.9 Hz), 6.88 (dd, 1H, J=8.6, 1.9 Hz), 5.93 (m, 1H), 3.83 (br s, 2H), 3.24-3.30 (m, 4H), 3.11-3.17 (m, 2H), 2.83 (ddd, 2H, J=12.0, 12.0, 2.3 Hz), 1.72 (dd, 2H, J=12.6, 2.3 Hz), 1.53 (m, 1H), 1.35-1.47 (m, 2H), 1.00 (d, 3H, J=6.3 Hz). Mass spectrum (ESI, m/z): Calcd. for C17H22N2O4S, 351.1 (M+H), found 351.0.

後処理

  1. temperatureWarmed to RT
  2. stirringthe mixture was stirred vigorously for 5 min
  3. customThe aqueous layer was separated
  4. washthe organic layer was washed with saturated aq NaHCO3 solution (10 mL), H2O (10 mL)
  5. dry with materialdried (Na2SO4)
  6. customRemoval of the solvent under reduced pressure

出典と根拠

ORDレコード
ord-53b145efe5624d79a1c671a3b8eca9cf
出典データセット
uspto-grants-2010_04
特許番号
US07705042B2

反応ノート

読み込み中…