HCID 10637344, compound → HCID 10753913, compound

HRID 2294524Notes

Reaction equation

HRID 2294524 reaction equation
[CH2:1]([O:8][C:9]1[C:14]([N+:15]([O-])=O)=[CH:13][C:12]([CH3:18])=[C:11]([CH3:19])[C:10]=1[Cl:20])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>CO.[Cu]Cl>[NH2:15][C:14]1[C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[C:10]([Cl:20])[C:11]([CH3:19])=[C:12]([CH3:18])[CH:13]=1

Participants

4

Reactant 1

HCID 10637344HCID 10637344, compound

Product 1

HCID 10753913HCID 10753913, compoundYield 79.4%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 887MethanolSolvent

Procedure

1-Benzyloxy-2-chloro-3,4-dimethyl-6-nitrobenzene (3.00 g, 10.3 mmol) was dissolved in MeOH (420 mL) and cooled to +2° C. Copper(I) chloride (6.11 g, 30.8 mmol) was added followed by KBH4 (3.88 g, 72.0 mmol) portionwise added at +2° to +4° C. during 1.5 h. The reaction mixture was stirred at +2° C. for 1 h and more KBH4 (400 mg, 7.41 mmol) was added. After 1 h at +2° C. additional KBH4 (120 mg, 2.22 mmol) was added and the stirring was continued for another 20 min. Filtration and evaporation of the solvent gave a residue which was extracted between EtOAc (400 mL) and water (75 mL). Drying (MgSO4) and evaporation afforded 2.94 of crude product. Purification by flash column chromatography (SiO2, CHCl3) yielded the title compound (2.14 g). Mp: 57°-58° C.; 1H NMR (DMSO-d6): δ 7.54 (d, J=6.5 Hz, 2H), 7.42-7.34 (m, 3H), 6.52 (s, 1H), 4.83 (s, 2H), 4.79 (s, 2H), 2.12 (s, 6H); 13C NMR (DMSO-d6): δ 140.00, 138.91, 137.30, 133.00, 128.27, 128.22, 127.91, 127.33, 121.23, 115.35, 72.73, 20.24, 15.45; MS (EI, 70 eV): m/z (rel.int.) 286/284 (M+23,42/100).

Workup

  1. temperaturecooled to +2° C
  2. additionportionwise added at +2° to +4° C. during 1.5 h
  3. waitthe stirring was continued for another 20 min
  4. filtrationFiltration and evaporation of the solvent
  5. customgave a residue which
  6. extractionwas extracted between EtOAc (400 mL) and water (75 mL)
  7. customDrying
  8. custom(MgSO4) and evaporation
  9. customafforded 2.94 of crude product
  10. customPurification by flash column chromatography (SiO2, CHCl3)

Sources & evidence

ORD record
ord-16e88c5bec544626ae230895bffc3f21
Source dataset
uspto-grants-1997_11
Patent number
US05688945

Reaction notes

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