Sulfuric Acid → 1-(3-Aminotricyclo[3.3.1.03,7]non-1-yl)pyrrolidin-2-one

HRID 1015525Notes

Reaction equation

[O:1]=[C:2]1[CH2:6][CH2:5][CH2:4][N:3]1[C:7]12[CH2:15][CH:11]3[CH2:12][CH:13]([CH2:14]1)[C:9](C(O)=O)([CH2:10]3)[CH2:8]2.OS(O)(=O)=O.[N-:24]=[N+]=[N-].[Na+]>C(Cl)(Cl)Cl.O>[NH2:24][C:9]12[CH2:10][CH:11]3[CH2:15][C:7]([N:3]4[CH2:4][CH2:5][CH2:6][C:2]4=[O:1])([CH2:14][CH:13]1[CH2:12]3)[CH2:8]2

Participants

Conditions

Temperature: 45 °C

Procedure

To a stirred solution of the acid obtained in step II (0.5 g, 2.0 mmol) in CHCl3 (21 mL) at room temperature was added conc. H2SO4 (1.0 mL, 20 mmol) followed by NaN3 (0.39 g, 6.0 mmol) in portions over a period of 30 min., so that the temperature of the reaction did not rise above 40° C. The reaction was warmed to 45° C. and stirred for 2 h, then cooled to ice bath temperature, diluted with water and extracted with EtOAc. The aqueous layer was basified by adding 50% NaOH solution and extracted with CHCl3. The combined organic layer was washed with brine, dried over Na2SO4 and the solvent was removed under reduced pressure to obtain 1-(3-aminotricyclo[3.3.1.03,7]non-1-yl) pyrrolidin-2-one as an off-white solid (0.25 g) in 74% yield. m/z (M+1) 221; 1H NMR (CDCl3) 300 MHz δ 3.41 (t, J=7.0 Hz, 2H), 2.46 (dd, J=2.4, 10.3 Hz, 1H), 2.38-2.28 (m, 1H), 2.30 (t, J=8.3 Hz, 2H), 2.16-1.82 (m, 9H), 1.78 (dd J=2.6, 10.8 Hz, 1H), 1.66-1.58 (m, 1H), 1.51 (dd, J=2.5, 10.8 Hz, 1H).

Workup

customdid not rise above 40° C
temperaturecooled to ice bath temperature
extractionextracted with EtOAc
additionby adding 50% NaOH solution
extractionextracted with CHCl3
washThe combined organic layer was washed with brine
dry with materialdried over Na2SO4
customthe solvent was removed under reduced pressure

Sources & evidence

ORD record: ord-53e282da56c54261a393ce88f242d964
Source dataset: uspto-grants-2011_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07985759B2

Reaction notes

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