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

HRID 646911Notes

Reaction equation

HRID 646911 reaction equation
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

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-53b145efe5624d79a1c671a3b8eca9cf
Source dataset
uspto-grants-2010_04
Patent number
US07705042B2

Reaction notes

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