2-Bromo-4'-nitroacetophenone → alpha-(4-Picolylthio)p-nitroacetophenone

HRID 485057Notes

Reaction equation

HRID 485057 reaction equation
C[O-].[Na+].[N:4]1[CH:9]=[CH:8][C:7]([CH2:10][SH:11])=[CH:6][CH:5]=1.Br[CH2:13][C:14]([C:16]1[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=1)=[O:15]>C(O)C>[N:4]1[CH:9]=[CH:8][C:7]([CH2:10][S:11][CH2:13][C:14]([C:16]2[CH:17]=[CH:18][C:19]([N+:22]([O-:24])=[O:23])=[CH:20][CH:21]=2)=[O:15])=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 668402-Bromo-4'-nitroacetophenoneHCID 10942334Sodium MethoxideHCID 13092602Pyridin-4-ylmethanethiol

Product 1

HCID 20271287alpha-(4-Picolylthio)p-nitroacetophenone

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Under a nitrogen atmosphere, sodium methoxide (0.52 g., 9.6 mmoles) was dissolved in 15 ml. of absolute ethanol and cooled to 0°-5° C. 4-Picolyl mercaptan (1.2 g., 9.6 mmoles) in 15 ml. of ethanol was added over 5 minutes time. Alpha-bromo-p-nitro-acetophenone (2.3 g., 9.6 mmoles) in 20 ml. of warm ethanol was then added over 5 minutes, the mixture was warmed to room temperature and left to stir for approximately 16 hours. The reaction mixture was filtered and the filtrate concentrated to an oil (4.3 g.). The oil was chromatographed on 175 g. of silica gel with 1:1 hexane:ethyl acetate as eluant. Product-containing fractions were combined and evaporated to yield alpha-(4-picolylthio)-p-nitro-acetophenone [1.40 g.; oil; pnmr/CDCl3 /TMS/delta: 6.5 (3, 4H), 2.7 (d, 2H), 1.9 (d, 4H), 1.5 (d, 2H); mass spectra: m/e calcd.: 288; found: 288, 242, 165, 150, 138, 124, 104, 92, 76, 65, 39; ir (film): 3-3.5, 5.95, 6.25, 6.55, 7.35, 7.85, 11.70,μ].

Workup

  1. waitleft
  2. filtrationThe reaction mixture was filtered
  3. concentrationthe filtrate concentrated to an oil (4.3 g.)
  4. customThe oil was chromatographed on 175 g
  5. customevaporated

Sources & evidence

ORD record
ord-6f0d5520f9814793b8c87a202d5766af
Source dataset
uspto-grants-1985_08
Patent number
US04535084

Reaction notes

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