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

HRID 646911노트

반응식

HRID 646911 반응식
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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 6344Dichloromethane용매2회

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온도
-78 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-53b145efe5624d79a1c671a3b8eca9cf
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07705042B2

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