1,2-Dibromoethane → 2,4-Dichloro-6,6-dimethyl-8,9-dihydro-6H-[1,4]oxazino[4,3-e]purine

HRID 334160Notes

Reaction equation

C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:8][CH2:9]Br.[Cl:11][C:12]1[N:20]=[C:19]2[C:15]([N:16]=[C:17]([C:21]([OH:24])([CH3:23])[CH3:22])[NH:18]2)=[C:14]([Cl:25])[N:13]=1>CN(C=O)C>[Cl:25][C:14]1[C:15]2[N:16]=[C:17]3[N:18]([CH2:8][CH2:9][O:24][C:21]3([CH3:23])[CH3:22])[C:19]=2[N:20]=[C:12]([Cl:11])[N:13]=1

Participants

Conditions

Temperature: 100 °C

Procedure

Cesium carbonate (9.3 g, 28.5 mmol) and 1,2-dibromoethane (4.1 mL, 47.6 mmol) were added to a solution of 2-(2,6-dichloro-9H-purin-8-yl)-propan-2-ol (3.3 g, 13.36 mmol) in DMF (100 mL) and the reaction mixture was heated at 100° C. for 2 h, then partitioned between water and ethyl acetate. The organic extract was separated and washed with brine, then dried (MgSO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (SiO2, 0 to 10 to 20% ethyl acetate in cyclohexane) affording 1,3-Dichloro-8,8-dimethyl-5,6-dihydro-8H-7-oxa-2,4,4b,9-tetraaza-fluorene as a yellow solid (1.0 g, 27%). 1H NMR (400 MHz, CDCl3): δ 4.26 (2H, dd, J=6, 4 Hz), 4.19 (2H, dd, J=6, 4 Hz).

Workup

custompartitioned between water and ethyl acetate
extractionThe organic extract
customwas separated
washwashed with brine
dry with materialdried (MgSO4)
concentrationconcentrated in vacuo
customThe resulting residue was purified by column chromatography (SiO2, 0 to 10 to 20% ethyl acetate in cyclohexane)

Sources & evidence

ORD record: ord-1836ec3aa7704d408a23f42f00dcf74a
Source dataset: uspto-grants-2014_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08883799B2

Reaction notes

Loading…