Acrolein → 3-(2-Oxocyclohexyl)propanal
Reaction equation
C[C:2]1(C)[CH2:7][CH2:6][C:5](=[O:8])[CH2:4][CH2:3]1.[CH:10]([CH:12]=[CH2:13])=[O:11]>>[O:8]=[C:5]1[CH2:4][CH2:3][CH2:2][CH2:7][CH:6]1[CH2:13][CH2:12][CH:10]=[O:11]Participants
Procedure
The title compound 1 was prepared in the following way. ##STR18## Isobutyraldohyde was alkylated with methyl vinyl ketone via its pyrrolidine enamine, cyclized in acid, and then hydrogenated to give 4,4-dimethylcyclohexanone (2). Ketone 2 was alkylated with acrolein via its morpholline enamine then hydrolyzed to give 3-(2-oxocyclohexyl)propanal (3). Crude 3 was then purified through its diketal, cyclized in 7 N hydrochloric acid, and esterified to give 7,7-dimethylbicyclo(3.3.1)nonan-9-one-2-yl pivalate (4). Kettalization of 4 followed by alkaline hydrolysis, CrO,--pyridine oxidation, and alkylation with iodomethane and potassium t-butoxide yielded 3,3,7,7-tetramothyl-9,9-ethylenedioxybicyclo(3.3.1)nonan2one (5). When various attempts of Wolff-Kishner reduction failed, 5 was reduced to alcohol with lithium--ammonia then mesylated to give 3,3,7,7-tetramethyl-9,9-ethylenedioxybicyclo(3.3.1)nonan-2-exo-yl methanesulfonae (6). Lithium--ammonia reduction of 6 followed by acid hydrolysis afforded the title compound 1.
Sources & evidence
- ORD record
- ord-42fbff400e9f4975b6d603628cee6e8c
- Source dataset
- uspto-grants-1990_10
- Patent number
- US04963557
Reaction notes
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