Bromomethyl 4-methoxyphenyl ketone → alpha(4-Picolylthio)-p-methoxyacetophenone

HRID 485056Notes

Reaction equation

HRID 485056 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]([O:22][CH3:23])=[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:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=2)=[O:15])=[CH:6][CH:5]=1

Participants

5

Reactant 3

HCID 4965Bromomethyl 4-methoxyphenyl ketoneHCID 10942334Sodium MethoxideHCID 13092602Pyridin-4-ylmethanethiol

Product 1

HCID 13490317alpha(4-Picolylthio)-p-methoxyacetophenoneYield 72.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Under a nitrogen atmosphere sodium methoxide (0.62 g., 11.4 mmoles) was dissolved in approximately 15 ml. of absolute ethanol and cooled in an ice bath. 4-Picolyl mercaptan (1.43 g., 11.4 mmoles) in approximately 3 ml. of absolute ethanol was added over approximately 5 minutes. After stirring for an additional 10 minutes, a slurry of alpha-bromo-p-methoxyacetophenone (2.62 g., 11.4 mmoles) in approximately 5 ml. of absolute ethanol was added over 10 minutes. The mixture was allowed to warm to room temperature and stirred for approximately 16 hours. The reaction mixture was concentrated to an oil containing solids, triturated with chloroform, salts removed by filtration and reconcentration to an oil (3.6 g.). The oil was chromatographed on 120 g. of silica gel with chloroform as eluant. Product containing fractions were combined and stripped to an oil which crystallized on trituration with cold ether. Filtration gave alpha(4-picolylthio)-p-methoxyacetophenone [2.27 g.; m.p. 64-65° C.; ir (KBr): 3-3.5, 5.95, 6.25, 7.95, 8.55, 12.0 and 12.2,μ mass spectra: m/e calcd: 273, found: 273, 150, 135, 124, 107, 92; pnmr/CDCl3 /TMS/delta: 6.35 (s, 2H), 6.3 (s, 2H), 6.1 (s, 3H), 3.1 (d, 2H), 2.7 (d, 2H), 2.0 (d, 2H), 1.4 (d, 2H)].

Workup

  1. stirringstirred for approximately 16 hours
  2. concentrationThe reaction mixture was concentrated to an oil
  3. additioncontaining solids
  4. customtriturated with chloroform, salts
  5. customremoved by filtration and reconcentration to an oil (3.6 g.)
  6. customThe oil was chromatographed on 120 g
  7. additionProduct containing fractions
  8. customcrystallized on trituration with cold ether
  9. filtrationFiltration

Sources & evidence

ORD record
ord-98959c8ca08341dda887b646ae092eaf
Source dataset
uspto-grants-1985_08
Patent number
US04535084

Reaction notes

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