Ammonia → HCID 69772399, compound

HRID 1529846Notes

Reaction equation

[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][CH2:8][C@:9]12[CH2:17][CH2:16][C:15]3[C:18]4[CH:19]=[CH:20][C:21]([O:26][CH3:27])=[CH:22][C:23]=4[CH2:24][CH2:25][C:14]=3[C@@H:13]1[CH2:12][CH2:11][CH:10]2[OH:28].N.[Li].[NH4+].[Cl-]>NC1C=CC=CC=1.C1COCC1>[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][CH2:8][C@:9]12[CH2:17][CH2:16][C@@H:15]3[C:18]4[CH:19]=[CH:20][C:21]([O:26][CH3:27])=[CH:22][C:23]=4[CH2:24][CH2:25][C@H:14]3[C@@H:13]1[CH2:12][CH2:11][CH:10]2[OH:28]

Participants

Conditions

Temperature: -20 °C

Procedure

A solution of 51 (46.9 g, 0.12 mol) in aniline (250 mL) and dry THF (2 L) was added to ammonia (800 mL). Lithium metal (4.9 g, 0.72 mol) was added in pieces, and the blue mixture was stirred at −20° C. At −78° C., a solution of saturated aqueous NH4Cl was added upon depletion of lithium and the ammonia was allowed to evaporate. The solution was extracted with ethyl acetate (3×500 mL), water (500 mL), and brine. The organic phase was dried over anhydrous magnesium sulfate, the solvent was removed in vacuo, and the product 52 was purified by column chromatography on SiO2 (hexanes to hexanes-acetone/8-3) to provide 48.3 g (82%, over three steps from 49). 1H NMR (400 MHz, acetone-d6) δ 1.11-2.36 (m, 14H), 2.85 (m, 2H), 3.25-4.00 (m, 15H), 4.63 (m, 2H), 6.63 (m, 1H), 6.69 (m, 1H), 7.20 (d, J=8.6 Hz, 1H) ppm.

Workup

customto evaporate
extractionThe solution was extracted with ethyl acetate (3×500 mL), water (500 mL), and brine
dry with materialThe organic phase was dried over anhydrous magnesium sulfate
customthe solvent was removed in vacuo
customthe product 52 was purified by column chromatography on SiO2 (hexanes to hexanes-acetone/8-3)
customto provide 48.3 g (82%, over three steps from 49)

Sources & evidence

ORD record: ord-ae8ffab21b37499a988729957fdf68eb
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09090651B2

Reaction notes

Loading…