Hydrochloric Acid → 1-Chloro-7-methoxynaphthalene

HRID 1830666

Reaction equation

HRID 1830666 reaction equation
N(OC(C)(C)C)=O.[CH3:8][O:9][C:10]1[CH:19]=[C:18]2[C:13]([CH:14]=[CH:15][CH:16]=[C:17]2N)=[CH:12][CH:11]=1.[ClH:21]>C(#N)C>[Cl:21][C:17]1[CH:16]=[CH:15][CH:14]=[C:13]2[C:18]=1[CH:19]=[C:10]([O:9][CH3:8])[CH:11]=[CH:12]2

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 2358177-Methoxynaphthalen-1-amine

Product 1

HCID 220481521-Chloro-7-methoxynaphthaleneYield 41%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

CuCl2 (4.6 g, 24.6 mmol) and t-butyl nitrite (4.46 g, 43.3 mmol), were added to acetonitrile (125 mL) at 0° C. To this mixture was slowly added a solution of 7-methoxynaphthylamine (4.99 g, 28.8 mmol) in acetonitrile (25 mL). The reaction was allowed to warm to room temperature, stirred with HCl (400 mL of 2N solution) and extracted with ethyl acetate (3×200 mL). The combined organic layers were washed with 2N HCl, dried over sodium sulfate, filtered, evaporation of the solvent, and purification on a silica column (hexanes) yielded 2.27 g (41%) of an orange liquid. An analytical sample was further purified by reverse phase preparative HPLC to yield the title compound as a yellow solid: mp 32–34° C.;1H NMR (CDCl3): δ 3.98 (3H, s), 7.20 (1H, dd, J=2.52 Hz, J=8.96 Hz), 7.22–7.27 (1H, m), 7.52 (1H, d, J=2.47 Hz), 7.55 (1 h, d, J=7.47 Hz), 7.69 (1H, d, J=8.15 Hz), 7.75 (1H, d, J=8.95 Hz); MS m/z 191/193 (M−H)−.

Workup

  1. extractionextracted with ethyl acetate (3×200 mL)
  2. washThe combined organic layers were washed with 2N HCl
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporation of the solvent, and purification on a silica column (hexanes)

Sources & evidence

ORD record
ord-f3b4cc3c0b8b4bf482da582e31089b3f
Source dataset
uspto-grants-2006_06
Patent number
US07067524B2

Linked notes

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