4-Penten-2-one, 4-methyl- → 1-(2-Chloro-3-methylphenyl)propan-2-one

HRID 514108Notes

Reaction equation

HRID 514108 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[C:3]=1[Cl:9].C([Sn](CCCC)(CCCC)OC)CCC.CC(=C)[CH2:27][C:28](=[O:30])[CH3:29].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>Cl[Pd]Cl.C1(C)C=CC=CC=1>[Cl:9][C:3]1[C:4]([CH3:8])=[CH:5][CH:6]=[CH:7][C:2]=1[CH2:27][C:28](=[O:30])[CH3:29]

Participants

7

Reactant 4

HCID 195434-Penten-2-one, 4-methyl-HCID 80271Tri-o-tolylphosphineHCID 133481341-Bromo-2-chloro-3-methylbenzeneHCID 16683411Tributyltin methoxide

Product 1

HCID 671262301-(2-Chloro-3-methylphenyl)propan-2-oneYield 80%

Reagents, catalysts & solvents 2

HCID 24290Palladium ChlorideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A Smith process vial was charged with 1-bromo-2-chloro-3-methylbenzene (528 mg, 2.57 mmol, 1 eq.), tributylmethoxytin (1.11 mL, 1.5 eq.), 4-methylpent-4-en-2-one (0.42 mL, 1.5 eq.), PdCl2 (23 mg, 5%) and tri(o-tolyl)phosphine (79 mg, 10%), toluene (1 mL) was added and mixture sparged with nitrogen for 10 minutes and then heated in oil bath at 100° C. for 5 hours. The reaction mixture was diluted with ethyl acetate and washed with brine, dried (MgSO4), filtered, concentrated and purified by flash column chromatography (silica gel, 0 to 20% ethyl acetate/hexanes) to 1-(2-chloro-3-methylphenyl)propan-2-one (375 mg, 80% yield). 1H-NMR: 400 MHz, (CDCl3) δ: 7.19-7.02 (m, 3H), 3.82 (s, 2H), 2.38 (s, 3H), 2.18 (s, 3H).

Workup

  1. additionwas added
  2. custommixture sparged with nitrogen for 10 minutes
  3. additionThe reaction mixture was diluted with ethyl acetate
  4. washwashed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-39b2c77ff6f743c682864973eeefaea2
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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