Hydrochloric Acid → HCID 22716427, compound

HRID 1582879Notes

Reaction equation

HRID 1582879 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5](OC)=[CH:4][C:3]=1[C:10]1[CH:11]=[C:12]2[C:17](=[CH:18][CH:19]=1)[CH:16]=[C:15]([O:20][CH3:21])[C:14]([O:22][CH3:23])=[CH:13]2.Cl.N([O-])=O.[Na+].O>C(O)(=O)C>[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:10]1[CH:11]=[C:12]2[C:17](=[CH:18][CH:19]=1)[CH:16]=[C:15]([O:20][CH3:21])[C:14]([O:22][CH3:23])=[CH:13]2

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 22716431HCID 22716431, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 22716427HCID 22716427, compoundYield 28.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

6-(2-Amino-5-methoxyphenyl)-2,3-dimethoxynaphthalene (33) (60 mg, 0.20 mmol) was dissolved in acetic acid (1.5 mL) and concentrated hydrochloric acid (0.3 mL). The solution was cooled in an ice bath and diazotized by dropwise addition of a solution of sodium nitrite (0.12 g in 1.2 mL water). The resulting diazonium solution was allowed to rise to room temperature slowly and left overnight. To the resulting red solution with some precipitate, 50 mL water was added and then extracted with ethyl acetate (40 mL×3). The organic layers were combined and washed with diluted sodium hydroxide solution first, then with water and brine. Dried with anhydrous sodium sulfate and evaporated in vacuo. The crude product was purified by column chromatography on silica gel using 35:65 hexanes:ethyl acetate to give the pure 5 (16 mg) in 26% yield; mp 215-217° C.; IR (KBr) 2987, 1617, 1504, 1486, 1394, 1277, 1231, 1167 cm−1; UV (MeOH) 288, 262, 232 nm (log ε=4.71, 4.66, 4.58); 1H NMR (CDCl3) δ4.07 (3H, s), 4.09 (3H, s), 4.22 (1H, s), 7.29 (1H, s), 7.46 (1H, dd, J1=9.1, J2=2.6), 7.72 (1H, J=2.5), 7.99 (1H, d, J=8.9), 8.20 (1H, d, J=9.0), 8.60 (1H, d, J=9.1), 9.17 (1H, s); 13C NMR δ56.31, 56.51, 56.90, 100.27, 104.61, 107.73, 117.00, 118.66, 121.31, 124.25, 126.98, 129.09, 131.40, 133.34, 141.76, 143.70, 151.23, 151.31, 161.95; HRMS (EI) calcd for C19H16N2O3 m/z: 320.1161; found: 320.1144.

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. customto rise to room temperature
  3. extractionextracted with ethyl acetate (40 mL×3)
  4. washwashed with diluted sodium hydroxide solution first
  5. dry with materialDried with anhydrous sodium sulfate
  6. customevaporated in vacuo
  7. customThe crude product was purified by column chromatography on silica gel using 35:65 hexanes

Sources & evidence

ORD record
ord-9a3920617f1941c7b75d38bab76c2c7f
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

Loading…