Hydrochloric Acid → HCID 135848689, compound

HRID 2056243Notes

Reaction equation

HRID 2056243 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([OH:17])=[C:6]([C:8]2[N:13]=[C:12]([C:14]([OH:16])=[O:15])[CH:11]=[CH:10][CH:9]=2)[CH:7]=1.[N+:18]([O-])([OH:20])=[O:19].Cl.N([O-])=O.[Na+].C(=O)([O-])O.[Na+]>C(O)(=O)C.O.C(O)C>[Cl:1][C:2]1[CH:3]=[C:4]([N+:18]([O-:20])=[O:19])[C:5]([OH:17])=[C:6]([C:8]2[N:13]=[C:12]([C:14]([OH:16])=[O:15])[CH:11]=[CH:10][CH:9]=2)[CH:7]=1

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 944Nitric AcidHCID 516892Sodium BicarbonateHCID 23668193Sodium NitriteHCID 135848690HCID 135848690, compound

Product 1

HCID 135848689HCID 135848689, compoundYield 29%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 962WaterSolvent3×

Conditions

Temperature
5 °C

Procedure

To the solution of 6-(5-chloro-2-hydroxyphenyl)-pyridine-2-carboxylic acid; (2.3 g, 10.1 mmol) in 100 ml acetic acid; was added 1 ml fuming nitric acid; and stirred at 35° C. to 40° C. for half an hour. The reaction mixture was diluted with water and adjusted pH to 2.5. The resulting preciptation was collected, washed and dried to give solid (2.74 g; 78%, three steps). MS(ES) m/z 295 [M+H]. d) 3-Aza-3′-{N′-[1-(4-tert-butylphenyl)-3-methyl-5-oxo-1,5-dihydropyrazol-4-ylidene]hydrazino}-2′-hydroxybiphenyl-5-carboxylic acid; Following the procedure of Example 1c), except substituting the compound of 4c) for the compound of 1b), the crude product was isolated. A suspension of the crude product (0.0015 mol.) in 1M aqu. hydrochloric acid; (25.0 mL) was cooled to 5° C. then treated dropwise with a solution of sodium nitrite (0.11 g; 0.0015 mol.) in water (5.0 mL). The yellow mixture was stirred at 5° C. for a further 10 min. then treated in one portion with the compound from Example 3a) (0.34 g, 0.0015 mol.) followed by the portion-wise addition of sodium hydrogen carbonate and ethanol ensuring the final pH of the reaction mixture is approximately 7-8. The red solution was then stirred at room temperature for 24 h. The mixture was filtered to give a red solid which was slurried in water (50.0 mL) and then acid;ified with concentrated hydrochloric acid;. Filtration afforded the title compound (0.2 g; 29%) as a powder. 1H NMR (300 MHz, d6-DMSO) δ 13.8 (br, 2H), 9.9 (s, 1H), 9.08 (s, 1H), 8.9 (s, 1H), 8.4 (s, 1H), 7.82 (d, J=7.7 Hz, 2H), 7.75 (d, J=7.9 Hz, 1H), 7.50 (d, J=7.0 Hz, 2H), 7.20 (m, 2H), 2.34 (s, 3H), 1.32(s, 9H) MS(ES) m/z 472 (M+H)+.

Workup

  1. additionwas added 1 ml
  2. customThe resulting preciptation was collected
  3. washwashed
  4. customdried
  5. customto give solid (2.74 g; 78%, three steps)
  6. customwas isolated
  7. stirringThe yellow mixture was stirred at 5° C. for a further 10 min.
  8. stirringThe red solution was then stirred at room temperature for 24 h
  9. filtrationThe mixture was filtered
  10. customto give a red solid which
  11. filtrationFiltration

Sources & evidence

ORD record
ord-4a61be6c49d240d5a5d22e5417c67699
Source dataset
uspto-grants-2008_02
Patent number
US07335649B2

Reaction notes

Loading…