Sodium Iodide → 1-(2-Methanesulfonyl-ethyl)-4-(3-nitro-phenyl)-1,2,3,6-tetrahydro-pyridine

HRID 472503Notes

Reaction equation

HRID 472503 reaction equation
C(O[C:6]([N:8]1[CH2:13][CH:12]=[C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=2)[CH2:10][CH2:9]1)=O)(C)(C)C.FC(F)(F)C(O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].[I-].[Na+].ClC[CH2:40][S:41]([CH3:44])(=[O:43])=[O:42]>ClCCl.O>[CH3:40][S:41]([CH2:44][CH2:6][N:8]1[CH2:13][CH:12]=[C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([N+:20]([O-:22])=[O:21])[CH:15]=2)[CH2:10][CH2:9]1)(=[O:43])=[O:42]

Participants

8

Reactant 5

HCID 5238Sodium IodideHCID 6422Trifluoroacetic acidHCID 10796Cesium carbonateHCID 3035331-Chloro-2-methanesulfonylethaneHCID 15751429Tert-butyl 4-(3-nitrophenyl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 674814071-(2-Methanesulfonyl-ethyl)-4-(3-nitro-phenyl)-1,2,3,6-tetrahydro-pyridine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

203 a) To a solution of 4-(3-nitro-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (0.50 g, 1.6 mmol) in dichloromethane (3 mL) was added trifluoroacetic acid (1.2 mL, 16 mmol). The mixture was stirred at room temperature for 2 hours then the volatiles were evaporated. The residue was dissolved in N,N-dimethylformamide (5 mL). Cesium carbonate (0.60 g, 1.8 mmol), sodium iodide (25.0 mg, 0.167 mmol) and 1-chloro-2-methanesulfonyl-ethane (0.26 g, 1.8 mmol) were added. The mixture was heated at 50° C. for 18 hours then cooled to room temperature and water (30 mL) was added. The mixture was extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with water (2×20 mL) and saturated aqueous sodium chloride (20 mL), dried over magnesium sulfate, filtered and evaporated. 1-(2-Methanesulfonyl-ethyl)-4-(3-nitro-phenyl)-1,2,3,6-tetrahydro-pyridine was isolated as an orange viscous oil (0.381 g, 75%). 1H NMR (400 MHz, CDCl3, δ, ppm): 8.23 (s, 1H), 8.11 (d, J=8.0 Hz, 1H), 7.70 (d, J=8.0 Hz, 1H), 7.50 (t, J=8.0 Hz, 1H), 6.23 (s, 1H), 3.27 (s, 2H), 3.23 (t, J=6.5 Hz, 2H), 3.07-3.01 (m, 5H), 2.82 (t, J=5.5 Hz, 2H), 2.61 (br s, 2H). MS=311 (MH)+.

Workup

  1. customthe volatiles were evaporated
  2. dissolutionThe residue was dissolved in N,N-dimethylformamide (5 mL)
  3. temperatureThe mixture was heated at 50° C. for 18 hours
  4. temperaturethen cooled to room temperature
  5. extractionThe mixture was extracted with ethyl acetate (3×20 mL)
  6. washThe combined organic layers were washed with water (2×20 mL) and saturated aqueous sodium chloride (20 mL)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-b0ac22b3486c4990821140dbe6ef7d87
Source dataset
uspto-grants-2014_01
Patent number
US08633173B2

Reaction notes

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