Iodine → 8-Amino-2-iodo-1-methyl-4,5-dihydro-1H-1,7,9-triaza-cyclopenta[a]naphthalene-3-carboxylic acid ethyl ester

HRID 222129Notes

Reaction equation

[CH2:1]([O:3][C:4]([C:6]1[C:10]2[CH2:11][CH2:12][C:13]3[C:18]([C:9]=2[N:8]([CH3:20])[C:7]=1C(O)=O)=[N:17][C:16]([NH2:19])=[N:15][CH:14]=3)=[O:5])[CH3:2].C([O-])(O)=O.[Na+].[I:29]I.[I-].[K+]>C(Cl)Cl.O>[CH2:1]([O:3][C:4]([C:6]1[C:10]2[CH2:11][CH2:12][C:13]3[C:18]([C:9]=2[N:8]([CH3:20])[C:7]=1[I:29])=[N:17][C:16]([NH2:19])=[N:15][CH:14]=3)=[O:5])[CH3:2]

Participants

Conditions

Temperature: 50 °C

Procedure

To a solution of 8-amino-1-methyl-4,5-dihydro-1H-1,7,9-triaza -cyclopenta[a]naphthalene-2,3-dicarboxylic acid 3-ethyl ester N7 (3.16 mmol) in a mixture of DCM (10 mL) and water (10 mL), under vigorous stirring at 50° C., NaHCO3 (9.48 mmol) and an aqueous solution (4 mL) of iodine (4.1 mmol) and potassium iodide (7.58 mmol) was added. The mixture was heated at 50° C. for 3 h, cooled to rt and the organic layer was separated and washed with aq NaHSO3. The organic phase was dried (Na2SO4) and evaporated to dryness. Chromatography on silica gel (eluant: AcOEt/hexane 7:3) afforded the title compound (30% yield). ESI (+) MS: m/z 399 (MH+). 1H NMR: 1.32 (t, J=7.07, 3H), 2.65 (t, J=7.68, 2H), 2.91 (t, J=7.68, 2H), 4.21 (s, 3H), 4.24 (q, J=7.07, 2H), 6.34 (bs, 2H), 8.02 (s, 1H).

Workup

temperatureThe mixture was heated at 50° C. for 3 h
temperaturecooled to rt
customthe organic layer was separated
washwashed with aq NaHSO3
dry with materialThe organic phase was dried (Na2SO4)
customevaporated to dryness

Sources & evidence

ORD record: ord-7446ed20b88d4893ac41e5e846dbc82b
Source dataset: uspto-grants-2012_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08207180B2

Reaction notes

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