Hydrochloric Acid → HCID 9888691, compound

HRID 1582883Notes

Reaction equation

HRID 1582883 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:4][C:3]=1[C:18]1[CH:19]=[C:20]2[C:25](=[CH:26][CH:27]=1)[CH:24]=[C:23]([O:28][CH3:29])[C:22]([O:30][CH3:31])=[CH:21]2.Cl.[N:33]([O-])=O.[Na+].O>C(O)(=O)C>[CH2:11]([O:10][C:5]1[C:6]([O:8][CH3:9])=[CH:7][C:2]2[N:1]=[N:33][C:19]3[C:18]([C:3]=2[CH:4]=1)=[CH:27][CH:26]=[C:25]1[CH:24]=[C:23]([O:28][CH3:29])[C:22]([O:30][CH3:31])=[CH:21][C:20]=31)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 22716425HCID 22716425, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 9888691HCID 9888691, compoundYield 67%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

6-(2-Amino-5-benzyloxy-4-methoxyphenyl)-2,3-dimethoxy-naphthalene 41 (35 mg, 0.084 mmol) was dissolved in acetic acid (0.65 mL) and concentrated hydrochloric acid (0.13 mL). The solution was cooled in an ice bath and diazotized by the dropwise addition of a solution of sodium nitrite (0.052 g in 0.52 mL water). The reaction mixture was allowed to warm slowly to room temperature and left for 1 day. To the resulting red solution containing some precipitate was added 50 mL water and the mixture was extracted with ethyl acetate (30 mL×3). The organic layers were combined and washed with diluted sodium hydroxide solution first, then with water and brine. The organic layer was dried using anhydrous sodium sulfate and evaporated in vacuo. The crude product was purified by column chromatography on silica gel using 20:80 hexanes:ethyl acetate to give the pure 42 (24 mg) in 67% yield; mp 244-246° C.; IR (KBr) 2935, 1621, 1507, 1466, 1307, 1269, 1234, 1206, 1168 cm−1; 1H NMR (CDCl3) δ4.07 (3H, s), 4.14 (3H, s), 4.21 (3H, s), 5.40 (2H, s), 7.25 (1H, s), 7.37-7.60 (5H, m), 7.91 (1H, d, J=9.0), 7.97 (1H, s), 8.01 (1H, d, J=9.0), 9.11 (1H, s); 13C NMR δ56.48, 56.86, 56.91, 71.64, 101.69, 104.43, 107.82, 109.58, 116.84, 118.19, 118.81, 126.95, 127.97, 128.34, 128.90, 129.34, 131.51, 136.31, 141.61, 144.52, 151.00, 151.14, 152.31, 152.93; HRMS (EI) calcd for C26H22N2O4 m/z: 426.1580; found: 426.1577.

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. additionTo the resulting red solution containing some precipitate
  3. extractionthe mixture was extracted with ethyl acetate (30 mL×3)
  4. washwashed with diluted sodium hydroxide solution first
  5. customThe organic layer was dried
  6. customevaporated in vacuo
  7. customThe crude product was purified by column chromatography on silica gel using 20:80 hexanes

Sources & evidence

ORD record
ord-61e60084857b494b88d769f0c6d17e5c
Source dataset
uspto-grants-2004_05
Patent number
US06740650B2

Reaction notes

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