Phosphorus oxychloride → 4-chlorobenzo[4,5]thieno[2,3-d]pyriMidine

HRID 1526495Notes

Reaction equation

[C:1]12[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[S:8][C:7]1[C:2]2=[C:3](O)[N:4]=[CH:5][N:6]=1.O=P(Cl)(Cl)[Cl:17]>O1CCOCC1>[Cl:17][C:3]1[N:4]=[CH:5][N:6]=[C:7]2[C:2]=1[C:1]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[S:8]2

Participants

Conditions

Temperature: 90 °C

Procedure

Into a 100-mL round-bottom flask, was placed a solution of 8-thia-4,6-diazatricyclo[7.4.0.0[2,7]]trideca-1(9),2,4,6,10,12-hexaen-3-ol (2.0 g, 9.89 mmol, 1.00 equiv) in 1,4-dioxane (15 mL) and POCl3 (4.5 g, 29.35 mmol, 2.97 equiv) under nitrogen. The resulting solution was stirred for 4 h at 90° C. The excess amount of POCl3 was removed under reduced pressure and the residue was diluted with DCM. The resulting mixture was poured into a cooled saturated aqueous sodium bicarbonate, extracted with DCM, dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:10) to afford 3-chloro-8-thia-4,6-diazatricyclo[7.4.0.0[2,7]]trideca-1(9),2,4,6,10,12-hexaene (0.9 g, 41%) as a white solid.

Workup

customInto a 100-mL round-bottom flask, was placed
customThe excess amount of POCl3 was removed under reduced pressure
additionthe residue was diluted with DCM
additionThe resulting mixture was poured into a cooled saturated aqueous sodium bicarbonate
extractionextracted with DCM
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated under vacuum
customThe residue was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:10)

Sources & evidence

ORD record: ord-4fe6c633d320422a8f2f746a7dc6bb4d
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09085586B2

Reaction notes

Loading…