Water → HCID 10664234, compound

HRID 1107636Notes

Reaction equation

HRID 1107636 reaction equation
[CH2:1]([O:8][C:9]1[C:18]2[C:13](=[CH:14][C:15](Br)=[CH:16][CH:17]=2)[CH:12]=[C:11]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:25]([Cu])#[N:26].O>CN(C=O)C>[CH2:1]([O:8][C:9]1[C:18]2[C:13](=[CH:14][C:15]([C:25]#[N:26])=[CH:16][CH:17]=2)[CH:12]=[C:11]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 962WaterHCID 10667770Ethyl 4-(benzyloxy)-7-bromonaphthalene-2-carboxylateHCID 178418546HCID 178418546, compound

Product 1

HCID 10664234HCID 10664234, compoundYield 74.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 12 (9.46 g, 27.2 mmol) in anhydrous DMF (12.6 mL) under Ar was treated with CuCN (2.92 g, 32.6 mmol, 1.2 equiv) and the mixture was warmed at reflux for 20 h. The reaction mixture was cooled to 25° C. and poured into 250 mL of H2O to which FeCl3 (5.29 g, 32.6 mmol, 1.2 equiv) was added with swirling. The solution was extracted with EtOAc (3×200 mL) and the combined organic layers were washed with saturated aqueous NaCl, dried (MgSO4) and concentrated. Recrystallization from 20% EtOAc-hexane provided 13 (6.70 g, 9.00 g theoretical, 74%) as a white solid. Chromatography (SiO2, 4×20 cm, 10% EtOAc-hexane) of the crystallization mother liquors afforded additional 13 (2.00 g, 22%, 96% combined) as white solid: mp 125° C. (needles, EtOH); 1H NMR (CDCl3, 250 MHz) δ8.43 (d, 1H, J=8.7 Hz), 8.29 (s, 1H), 8.25 (s, 1H), 7.69 (dd, 1H, J=1.6, 8.7 Hz), 7.66 (s, 1H), 7.56-7.39 (m, 5H), 5.32 (s, 2H), 4.46 (q, 2H, J=7.2 Hz), 1.46 (t, 3H, J=7.1 Hz); 13C NMR (CDCl3, 62.5 MHz) δ165.9, 154.3, 135.9, 134.6, 132.3, 129.8, 128.6, 128.3, 128.2, 127.8, 127.5, 123.8, 123.2, 118.6, 110.7, 106.9, 70.5, 61.5, 14.3; IR (KBr) vmax 2994, 2226, 1711, 1577, 1502, 1284, 1252, 1093, 1029, 916, 827 cm-1 ; FABHRMS (NBA) m/z 332.1276 (M+ +H, C21H17NO3 requires 332.1287).

Workup

  1. temperaturethe mixture was warmed
  2. temperatureat reflux for 20 h
  3. additionwas added
  4. extractionThe solution was extracted with EtOAc (3×200 mL)
  5. washthe combined organic layers were washed with saturated aqueous NaCl
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customRecrystallization from 20% EtOAc-hexane

Sources & evidence

ORD record
ord-5649c9fec26940c7a2f1f7ab7041f772
Source dataset
uspto-grants-2000_05
Patent number
US06060608

Reaction notes

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