Dimethylformamide → 8-Chloro-4,5-dihydro-6-oxa-1,3a,9-triaza-benzo[e]azulene-2-carboxylic acid amide

HRID 1530517Notes

Reaction equation

[Cl:1][C:2]1[CH:3]=[C:4]2[C:13](=[CH:14][N:15]=1)[C:12]1[N:8]([CH:9]=[C:10](I)[N:11]=1)[CH2:7][CH2:6][O:5]2.N([Si](C)(C)C)[Si](C)(C)C.C[N:27]([CH:29]=[O:30])C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:13](=[CH:14][N:15]=1)[C:12]1[N:8]([CH:9]=[C:10]([C:29]([NH2:27])=[O:30])[N:11]=1)[CH2:7][CH2:6][O:5]2

Participants

Conditions

Temperature: 70 °C

Procedure

To a solution of 12-chloro-4-iodo-9-oxa-3,6,13-triazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaene (10.0 g, 28.7 mmol) in dry DMF (300 mL) was added Pd(PPh3)2Cl2 (1.00 g, 1.44 mmol) and (Me3Si)2NH (86.1 mmol, 14.0 g). The mixture was stirred at 70° C. for 4 h under carbon monoxide atmosphere. After removal of the solvent, the residue was treated with ice-water. The solid was collected by filtration, dissolved in ethyl acetate (400 ml), dried over anhydrous Na2SO4, and concentrated to give 12-chloro-9-oxa-3,6,13-triazatricyclo[8.4.0.02,6]tetradeca-1(14),2,4,10,12-pentaene-4-carboxamide (7.20 g, 97% yield), which was used in the next step without further purification. LCMS (ESI) m/z: 265.1 [M+H+]

Workup

customAfter removal of the solvent
additionthe residue was treated with ice-water
filtrationThe solid was collected by filtration
dissolutiondissolved in ethyl acetate (400 ml)
dry with materialdried over anhydrous Na2SO4
concentrationconcentrated

Sources & evidence

ORD record: ord-ac2bedb8dab64b6ead0471e75ea814cb
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09090628B2

Reaction notes

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