Bicyclo[2.2.2]octane-2-methanol → HCID 21512477, compound
Reaction equation
[BH4-].[Na+].C12CCC(CC1)C([CH2:11][OH:12])C2.[ClH:13].[CH3:14][N:15]([CH2:17][CH:18]1[CH:23]2[CH2:24][CH2:25][CH:20]([CH2:21][CH2:22]2)[CH:19]1[C:26]1[CH:31]=[CH:30][C:29]([N+]([O-])=O)=[CH:28][CH:27]=1)[CH3:16]>>[ClH:13].[CH3:14][N:15]([CH2:17][CH:18]1[CH:23]2[CH2:24][CH2:25][CH:20]([CH2:21][CH2:22]2)[CH:19]1[C:26]1[CH:31]=[CH:30][C:29]([O:12][CH3:11])=[CH:28][CH:27]=1)[CH3:16]Participants
Procedure
Ethyl trans-2-p-methylphenylbicyclo[2,2,2]octane-3-carboxylate (0.025 mole) was added to lithium aluminium hydride (0.03 mole) in tetrahydrofuran (60 ml.) at 0°C. and after 3 hours, water was added and the mixture extracted with ether. Evaporation of the ether extract gave the corresponding bicyclo[2,2,2]oct-3-yl methanol as an oil. The latter was dissolved in dichloromethane (50 ml.) and methylamine (10 ml.) and methanesulphonyl chloride (3.6 g.) added at 0°C. After 2 hours, dimethylamine (25 ml. of a 33% solution in water) was added to the resultant methyl sulphonate and the mixture refluxed for 1 week. A large excess of water was added and the mixture extracted with ether. Evaporation of the dried ether extract yielded a solid which, on addition of ethanolic hydrochloric acid, gave N,N-dimethyl-2-p-methylphenylbicyclo[2,2,2]oct-3-yl methylamine hydrochloride as a white solid (2 g.) which had a satisfactory C, H, N and Cl analysis. Similarly, N,N-dimethyl-2-p-methoxyphenylbicyclo[2,2,2]oct-3-yl methylamine hydrochloride was prepared. Also by reduction of trans-2-p-nitrophenylbicyclo[2,2,2]octane-3-carboxyaldehyde, using sodium borohydride, followed by treatment of the resultant methanol as described above, N,N-dimethyl-2-p-nitrophenylbicyclo[2,2,2]oct-3-yl methylamine hydrochloride was obtained.
Workup
- customwas obtained
Sources & evidence
- ORD record
- ord-26fb4bf06f7a46d5b89a48f8616b64d2
- Source dataset
- uspto-grants-1976_09
- Patent number
- US03980785
Reaction notes
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