1-Adamantanecarbonyl chloride → Adamantane-1-carboxylic acid (R)-1-pyridin-4-yl-ethyl ester

HRID 234644Notes

Reaction equation

HRID 234644 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([C@H:7]([OH:9])[CH3:8])=[CH:3][CH:2]=1.C([Li])CCC.[C:15]12([C:25](Cl)=[O:26])[CH2:24][CH:19]3[CH2:20][CH:21]([CH2:23][CH:17]([CH2:18]3)[CH2:16]1)[CH2:22]2>C1COCC1.CCCCCC>[C:15]12([C:25]([O:9][C@@H:7]([C:4]3[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=3)[CH3:8])=[O:26])[CH2:22][CH:21]3[CH2:20][CH:19]([CH2:18][CH:17]([CH2:23]3)[CH2:16]1)[CH2:24]2

Participants

6

Reactant 3

HCID 989151-Adamantanecarbonyl chlorideHCID 11804747(1R)-1-(pyridin-4-yl)ethan-1-olHCID 178418339Butyllithium

Product 1

HCID 10827014Adamantane-1-carboxylic acid (R)-1-pyridin-4-yl-ethyl esterYield 88.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

The method followed that described in Example 1, but using (+)-(R)-1-(4-pyridyl)ethanol (369 mg, 3.0 mmol) in THF (12 ml), n-butyllithium (2.5 M, 1.2 ml, 3.0 mmol) in hexane, and 1-adamantanecarbonyl chloride (656 mg, 3.3 mmol) in THF (3 ml). Chromatography, on elution with petrol-ether-triethylamine 200:50:1, afforded the title compound (754 mg, 88%). [α]D +25.8° (c 1, CHCl3); IR νmax 1730 cm-1 ; 1H-NMR (CDCl3) δ1.50 (3H, d, J 6.6 Hz, CHCH3), 1.73 and 1.93 (12H, 2s, adamantyl CH2), 2.04 (3H, s, adamantyl CH), 5.80 (1H, q, J 6.6 Hz, OCH), 7.23 (2H, d, J 6.1 Hz, Py 3 and 5H), 8.58 (2H, d, J 6.1 Hz, Py 2 and 6H); MS m/z 285 (M+). By passing hydrogen chloride gas through a solution of the product in ether, the hydrochloride was obtained, m.p. 164°-166° C. Anal. Calcd: C, 67.17; H, 7.52; N, 4.35. Found: C, 67.58; H, 7.51; N, 4.36%.

Workup

  1. washChromatography, on elution with petrol-ether-triethylamine 200:50:1

Sources & evidence

ORD record
ord-c28e115d974a40dab842ce4caa6ac9a2
Source dataset
uspto-grants-1997_01
Patent number
US05595995

Reaction notes

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