Diisopropylamine → HCID 19097404, compound

HRID 486073Notes

Reaction equation

C(NC(C)C)(C)C.[Li]CCCC.[CH3:13][CH:14]1[C:19]2([CH3:23])[CH:20]([CH3:22])[CH2:21][CH:16]([CH:17]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:18]2)[N:15]1[CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.Cl[C:37]([O:39][CH2:40][CH3:41])=[O:38]>C1COCC1>[CH3:13][CH:14]1[C:19]2([CH3:23])[CH:20]([CH3:22])[CH2:21][CH:16]([C:17]([C:37]([O:39][CH2:40][CH3:41])=[O:38])([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:18]2)[N:15]1[CH2:29][C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1

Participants

Conditions

Temperature: -78 °C

Procedure

To a solution of diisopropylamine (13.2 mL, 94 mmol) in THF (175 mL) at -60° C. under nitrogen was added n-BuLi (36.2 mL, 94 mmol, 2.6M hexane). The mixture was stirred for 30 minutes, cooled to -78° C. and ethyl 3,4,8-trimethyl-2-(phenylmethyl)-2-azabicyclo[2.2.2]octane-6-carboxylate (26.8 g, 85 mmol) in THF (225 mL) was added. The mixture was stirred for 3 hours, then ethyl chloroformate (8.96 mL, 94 mmol) in THF (20 mL) was added dropwise. The mixture was stirred for 24 hours, quenched with saturated NH4Cl, and poured into water (1000 mL). The solution was extracted with ether (3X), and the organic layers were combined and dried over MgSO4. The ether layer was treated with charcoal and the solvent was removed in vacuo to afford 32.1 g (97%) of diethyl 3,4,8-trimethyl-2-(phenylmethyl)-2-azabicyclo-[2.2.2] octane-6,6-dicarboxylate as a golden oil.

Workup

stirringThe mixture was stirred for 3 hours
stirringThe mixture was stirred for 24 hours
customquenched with saturated NH4Cl
additionpoured into water (1000 mL)
extractionThe solution was extracted with ether (3X)
dry with materialdried over MgSO4
additionThe ether layer was treated with charcoal
customthe solvent was removed in vacuo

Sources & evidence

ORD record: ord-edfcc265121b465390e3739d7bf57109
Source dataset: uspto-grants-1994_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05290796

Reaction notes

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