Methyl acetoacetate → HCID 57733406, compound

HRID 1920732Notes

Reaction equation

Br[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]([Cl:11])[C:3]=1[C:4]([OH:6])=[O:5].[CH3:12][O:13][C:14](=[O:19])[CH2:15][C:16]([CH3:18])=[O:17].[H-].[Na+]>O.[Cu]Br>[Cl:11][C:7]1[CH:8]=[CH:9][CH:10]=[C:2]([CH:15]([C:14]([O:13][CH3:12])=[O:19])[C:16](=[O:17])[CH3:18])[C:3]=1[C:4]([OH:6])=[O:5]

Participants

Conditions

Temperature: 70 °C

Procedure

To a stirred mixture of 2-bromo-6-chlorobenzoic acid (20 g, 85 mmol), methylacetoacetate (310 ml, excess), and copper (I) bromide 12.2 g, 85 mmol) sodium hydride (8.5 g, 212 mmol, 60% in oil) was added by portions and then heated at 70° C. for 16 hours. The resulting mixture was diluted with water (600 ml) and extracted with diethyl ether (3×500 ml). Aqueous phase was acidified with 2M HCl and extracted with ethyl acetate (2×800 ml). The combined organic solution was washed with brine (100 ml), dried (Na2SO4) and evaporated. The obtained oil was treated with a hot mixture of ethyl acetate (20 ml) and heptane (200 ml) and decanted for 2 times, dried in vacuo to give 8 g of yellow-brown solid, yield 34%. 1H NMR (500 MHz, DMSO-d6): 1.73 (s, 3H), 3.6 (s, 3H), 7.24 (d, 1H), 7.44 (t, 2H), 7.5 (d, 1H), 12.85 (s, 1H, OH of enol form), 13.4 (br, 1H, CO2H).

Workup

additionwas added by portions
extractionextracted with diethyl ether (3×500 ml)
extractionextracted with ethyl acetate (2×800 ml)
washThe combined organic solution was washed with brine (100 ml)
dry with materialdried (Na2SO4)
customevaporated
additionThe obtained oil was treated with a hot mixture of ethyl acetate (20 ml) and heptane (200 ml)
customdecanted for 2 times
customdried in vacuo

Sources & evidence

ORD record: ord-4fd5c08e7d33495d8b1b161fe51f458c
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08173639B2

Reaction notes

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