Hydrochloric Acid → HCID 12083064, compound

HRID 1168537Notes

Reaction equation

HRID 1168537 reaction equation
Cl.[I:2][C:3]1[CH:4]=[C:5]2[C:10]3=[C:11]([C:13](=[O:21])[C:14]([C:16]([O:18]CC)=[O:17])=[CH:15][N:9]3[N:8]([CH3:22])[CH2:7][C:6]2(C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)[CH:12]=1>C(O)(=O)C>[I:2][C:3]1[CH:4]=[C:5]2[C:10]3=[C:11]([C:13](=[O:21])[C:14]([C:16]([OH:18])=[O:17])=[CH:15][N:9]3[N:8]([CH3:22])[CH2:7][CH2:6]2)[CH:12]=1

Participants

4

Reactant 2

HCID 313Hydrochloric Acid2×HCID 12083063HCID 12083063, compound

Product 1

HCID 12083064HCID 12083064, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Conditions

Temperature
110 °C

Procedure

A mixture of acetic acid (1 mL), 6N HCl (1 mL), and 3,3-di(tert-butyl) 8-ethyl 5-iodo-1-methyl-7-oxo-1,2-dihydro-3H,7H-pyrido[3,2,1-ij]cinnoline-3,3,8-tricarboxylate (Preparation 38, 0.165 g) is heated in an oil bath at 110° C. for 1.5 h. Additional acetic acid (1 mL) and 6N HCl (1 mL) is added and heating continued for 2 h. The reaction vessel is purged with a strong nitrogen stream while heating in the oil bath at 115° C. until dry solid remains. Dimethylsulfoxide (2 mL) is then added and the temperature raised to 150° C. for 1 h. The mixture is allowed to cool slowly overnight. The mixture is diluted with chloroform, treated with 2 g of silica gel, and concentrated at reduced pressure. The residue is chromatographed using 35 g of silica gel, packed and eluted with acetone/chloroform/methanol/acetic acid (3/6.6/0.4/0.5%), to obtain 53 mg (52%) of the title compound as a tan colored solid. Physical characteristics: 1H NMR (DMSO-d6) δ14.88, 8.80, 8.49, 8.18, 3.50, 3.15, 2.88; MS (ESI+) m/z 371 (M+H)+; TLC (silica gel GF): Rf=0.46 acetone/chloroform/methanol/acetic acid (3/6.5/0.5/0.5%).

Workup

  1. temperatureheating
  2. customThe reaction vessel is purged with a strong nitrogen stream
  3. temperaturewhile heating in the oil bath at 115° C.
  4. customuntil dry solid remains
  5. additionDimethylsulfoxide (2 mL) is then added
  6. temperaturethe temperature raised to 150° C. for 1 h
  7. temperatureto cool slowly overnight
  8. additionThe mixture is diluted with chloroform
  9. additiontreated with 2 g of silica gel
  10. concentrationconcentrated at reduced pressure
  11. customThe residue is chromatographed
  12. washeluted with acetone/chloroform/methanol/acetic acid (3/6.6/0.4/0.5%)

Sources & evidence

ORD record
ord-c0247f05f51f40088a70b0b0bbf13c23
Source dataset
uspto-grants-2003_09
Patent number
US06624159B2

Reaction notes

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