Phosphorus oxychloride → 5-Chloro-3,4-diazatricyclo(9.4.0.0,2,7)pentadeca-1(15),2(7),3,5,11,13-hexaene

HRID 1524206Notes

Reaction equation

HRID 1524206 reaction equation
[N:1]1[NH:2][C:3](=O)[CH:4]=[C:5]2[CH2:11][CH2:10][CH2:9][C:8]3[CH:12]=[CH:13][CH:14]=[CH:15][C:7]=3[C:6]=12.O=P(Cl)(Cl)[Cl:19]>>[Cl:19][C:3]1[N:2]=[N:1][C:6]2[C:7]3[CH:15]=[CH:14][CH:13]=[CH:12][C:8]=3[CH2:9][CH2:10][CH2:11][C:5]=2[CH:4]=1

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 141261586,7-dihydro-2H-benzo[6,7]cyclohepta[1,2-c]pyridazin-3(5H)-one

Product 1

HCID 141261595-Chloro-3,4-diazatricyclo(9.4.0.0,2,7)pentadeca-1(15),2(7),3,5,11,13-hexaene

Procedure

A mixture of the compound of formula (De), 6,7-dihydro-2H-benzo[6,7]cyclohepta[1,2-c]pyridazin-3(5H)-one (4.0 g, 19.3 mmol) and POCl3 (20 mL) was refluxed for 2 h. After cooling to ambient temperature, the volatiles were evaporated. The residue was poured into a mixture of ice water and sodium bicarbonate, CH2Cl2 (200 mL) was added to dissolve the solid. The layers were separated, and the aqueous layer was extracted with CH2Cl2 one more time. The combined organic layers were washed with brine. After being dried (MgSO4), filtered, and concentrated, the compound of formula (Df), 3-chloro-6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-c]pyridazine was obtained as a yellow solid (4.3 g, 99%), 1H NMR (300 MHz, CDCl3) δ: 7.82 (m, 1H), 7.45-7.24 (m, 4H), 2.59-2.51 (m, 4H), 2.27 (quant, J=6.9 Hz, 2H); LC-MS: purity: 100%; MS (m/e): 231 (MH+).

Workup

  1. temperaturewas refluxed for 2 h
  2. customthe volatiles were evaporated
  3. additionThe residue was poured into a mixture of ice water and sodium bicarbonate, CH2Cl2 (200 mL)
  4. additionwas added
  5. dissolutionto dissolve the solid
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with CH2Cl2 one more time
  8. washThe combined organic layers were washed with brine
  9. dry with materialAfter being dried (MgSO4)
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-7c4f5f8ed7624f4181d0885526a0d165
Source dataset
uspto-grants-2015_07
Patent number
US09079898B2

Reaction notes

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