P-Chloroacetophenone → HCID 86722006, compound

HRID 1398042Notes

Reaction equation

HRID 1398042 reaction equation
[CH3:1][C:2]1([CH3:11])[CH2:7][CH:6]([C:8](Cl)=[O:9])[CH2:5][CH2:4][O:3]1.CCOCC.[Mg+2].[Br-].[Br-].[CH3:20][C:21]([C:23]1[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=1)=[O:22].CCN(C(C)C)C(C)C>C(Cl)Cl>[Cl:29][C:26]1[CH:27]=[CH:28][C:23](/[C:21](/[OH:22])=[CH:20]/[C:8]([CH:6]2[CH2:5][CH2:4][O:3][C:2]([CH3:11])([CH3:1])[CH2:7]2)=[O:9])=[CH:24][CH:25]=1

Participants

6

Reactant 4

HCID 7467P-ChloroacetophenoneHCID 81531DiisopropylethylamineHCID 9903262Magnesium bromide diethyl etherateHCID 122964132,2-dimethyltetrahydro-2H-pyran-4-carbonyl chloride

Product 1

HCID 86722006HCID 86722006, compoundYield 58.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a mixture of 2,2-dimethyltetrahydro-2H-pyran-4-carbonyl chloride (0.55 g, 3.14 mmol), magnesium bromide diethyl etherate (1.35 g, 5.23 mmol), and 4-chloroacetophenone (0.34 mL, 2.62 mmol) in 12 mL of DCM at RT was added dropwise DIEA (1.45 mL, 7.85 mmol). The mixture was stirred overnight and then diluted with 50 mL of DCM and washed with 1N HCl (100 mL) and brine (100 mL). The organic layer was dried over Na2SO4, concentrated, and the crude product was purified by silica gel chromatography (Thomson Scientific 25-g cartridge, 2-20% EtOAc/heptane in 10 column volumes) to give 0.45 g (58%) of the title compound as a light orange solid. The NMR of this compound shows that it exists in the enone form in CDCl3.

Workup

  1. washwashed with 1N HCl (100 mL) and brine (100 mL)
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated
  4. customthe crude product was purified by silica gel chromatography (Thomson Scientific 25-g cartridge, 2-20% EtOAc/heptane in 10 column volumes)

Sources & evidence

ORD record
ord-2bc7bdd3851441c28a03dbcce7d8ca87
Source dataset
uspto-grants-2014_12
Patent number
US08901314B2

Reaction notes

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