Ammonia → (+/-)-4-Methyl-6-methoxy-9-iodo3,4,4a,5,10,10a-hexahydro-2H-naphto-[2,3-b][1,4]oxazine

HRID 975933Notes

Reaction equation

[CH3:1][N:2]1[CH2:7][CH2:6][O:5][CH:4]2[CH2:8][C:9]3[C:14]([CH2:15][CH:3]12)=[C:13]([O:16][CH3:17])[CH:12]=[CH:11][CH:10]=3.[I:18]I.N.CO.CCOC(C)=O>CC(O)=O.[Hg](OC(C)=O)OC(C)=O>[CH3:1][N:2]1[CH2:7][CH2:6][O:5][CH:4]2[CH2:8][C:9]3[C:14]([CH2:15][CH:3]12)=[C:13]([O:16][CH3:17])[CH:12]=[CH:11][C:10]=3[I:18]

Participants

Conditions

Temperature: 50 °C

Procedure

A solution of 4-methyl-6-methoxy-3,4,4a,5,10,10a-hexahydro-2H-naphtho[2,3-b][1,4]oxazine (0.37 g, 1.6 mmol) was dissolved in 7 ml of AcOH and heated to 50° C. To the solution of the amine was added a solution of Hg(OAc)2 (0.62 g, 19 mmol) and I2 (1.0 g, 3.8 mmol) in 30 ml of AcOH. The resulting solution was stirred for 1 h at 50° C. and 1.5 h at 25° C. The reaction mixture was filtered to remove mercury salts and concentrated in vacuo, yielding an oily residue which was subjected to column chromatography (5% NH3 sat'd MeOH-EtOAc) to yield 0.25 g (44%) of the desired product. 1H NMR (300 MHz, CDCl3): δ 2.04 (m, 1H), 2.32 (dd, 1H, J=11.0, 18.0 Hz), 2.41 (s, 3H), 2.49 (m, 1H), 2.62 (dd, 1H, J=11.0, 17.0 Hz), 2.76 (m, 1H), 3.12 (dd, 1H, J=6.0, 17.0 Hz), 3.33 (dd, 1H, J=5.6, 17.0 Hz), 3.56 (m, 1H), 3,81 (s, 3H), 3.88 (m, 2H), 6.47 (d, 1H, J=7.8 Hz), 7.66 (d, 1H, J=7.8 Hz).

Workup

filtrationThe reaction mixture was filtered
customto remove mercury salts
concentrationconcentrated in vacuo
customyielding an oily residue which

Sources & evidence

ORD record: ord-0c38da2546864177a396523135e649b7
Source dataset: uspto-grants-1997_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05610174

Reaction notes

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