tert-Butanol → 1-(2-Chlorophenyl)-4-(4-propoxyphenyl)-butane-1,4-dione

HRID 15011Notes

Reaction equation

HRID 15011 reaction equation
C(N(CC)CC)C.C(O)(C)(C)C.[CH2:13]([O:16][C:17]1[CH:22]=[CH:21][C:20]([C:23](=[O:25])[CH3:24])=[CH:19][CH:18]=1)[CH2:14][CH3:15].Br[CH2:27][C:28]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][C:31]=1[Cl:36])=[O:29]>C1C=CC=CC=1.[Cl-].[Cl-].[Zn+2]>[Cl:36][C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][C:30]=1[C:28](=[O:29])[CH2:27][CH2:24][C:23]([C:20]1[CH:19]=[CH:18][C:17]([O:16][CH2:13][CH2:14][CH3:15])=[CH:22][CH:21]=1)=[O:25]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 2601321-(4-Propoxyphenyl)ethan-1-oneHCID 27357852-Bromo-2'-chloroacetophenone

Product 1

HCID 160903391-(2-Chlorophenyl)-4-(4-propoxyphenyl)-butane-1,4-dioneYield 37.4%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolvent

Procedure

To a solution of 11.7 gm (85.6 mmol) of fused ZnCl2 in 20 mL of benzene was 10 added 8.50 mL (64 mmol) of triethylamine and 6.12 mL (64 mmol) of dry t-butanol. After dissolution at room temperature 11.45 gm (64 mmol) of 1-(4-propoxyphenyl) ethanone 100 and 10.0 gm (42.8 mmol) of 2-bromo-1-(2-chlorophenyl) ethanone 99. The mixture was allowed to stir at room temperature for 6 days. The solvents were removed at reduced pressure and the residue added to 100 mL of water. The aqueous phase was extracted with ethyl acetate (200 mL) twice. The combined organic layers were washed with water (150 mL), saturated brine, dried (Na2SO4) and the solvents removed at reduced pressure. Column chromatography of the residue using 2%-4%-8% ethyl acetate-hexanes yielded 5.3 gm (37%) of a light yellow solid. This was recrystallized from hot hexanes-ethyl acetate. 1H NMR (400 MHz, CDCl3) δ: 1.04 (t, 3H, J=7.42 Hz), 1.82 (m, 2H), 3.36 (m, 2H), 3.42 (m, 2H), 3.98 (t, 2H, J=6.5 Hz), 6.92 (d, 2H J=8.9 Hz), 7.38 (m, 3H), 7.64 (m, 1H), 7.97 (m, 2H).

Workup

  1. customThe solvents were removed at reduced pressure
  2. additionthe residue added to 100 mL of water
  3. extractionThe aqueous phase was extracted with ethyl acetate (200 mL) twice
  4. washThe combined organic layers were washed with water (150 mL), saturated brine
  5. dry with materialdried (Na2SO4)
  6. customthe solvents removed at reduced pressure

Sources & evidence

ORD record
ord-5d4d030b51634772a43068dfdc2d0ca3
Source dataset
uspto-grants-2010_06
Patent number
US07732457B2

Reaction notes

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