Potassium Carbonate → HCID 58203803, compound

HRID 1190266Notes

Reaction equation

[Cl:1][C:2]1[N:7]=[C:6](I)[C:5]([O:9][CH2:10][CH2:11][C:12]2[CH:16]=[CH:15][S:14][CH:13]=2)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[K+].[K+]>C(#N)C.[Cl-].C([N+](CC)(CC)CC)C.C(Cl)Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[O:9][CH2:10][CH2:11][C:12]3[CH:16]=[CH:15][S:14][C:13]=3[C:6]=2[N:7]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 6-chloro-2-iodo-3-(2-(thiophen-3-yl)ethoxy)pyridine (9.14 g, 25.0 mmol) in acetonitrile (150 mL) was added tetraethylammonium chloride (4.14 g, 25.0 mmol), potassium carbonate (6.91 g, 50.0 mmol) and triphenylphosphine (1.31 g, 5.00 mmol) The reaction mixture was degassed and then charged with N2 three times. Palladium acetate (0.561 g, 2.50 mmol) was added to the reaction mixture. The reaction mixture was stirred under N2 at 80° C. for 3 h. The reaction mixture was diluted with DCM then filtered through celite. The filtrate was concentrated to get the crude product, which was purified by column on silica gel (EtOAc/Hexanes=1:10) to afford 54.6 g of 9-Chloro-4,5-dihydro-6-oxa-1-thia-10-aza-benzo[e]azulene (Yield: 89%) 1H NMR (DMSO, 400 MHz): δ7.60 (d, J=5.2 Hz, 1H), 7.48 (d, J=6.0 Hz, 1H), 7.26 (d, J=6.0 Hz, 1H), 7.03 (d, J=5.2 Hz, 1H), 4.32 (t, J=4.4 Hz, 2H), 3.20 (t, J=4.4 Hz, 2H). LC-MS (ESI): m/z=238 [M+H]

Workup

customwas degassed
additioncharged with N2 three times
filtrationthen filtered through celite
concentrationThe filtrate was concentrated
customto get the crude product, which
customwas purified by column on silica gel (EtOAc/Hexanes=1:10)

Sources & evidence

ORD record: ord-ebfd2ac6e29243b6b60dc3bbec8cf5a2
Source dataset: uspto-grants-2014_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08673952B2

Reaction notes

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