Hydroxyamine hydrochloride → 7-Bromo-9,9-diethylfluorene-2-carbonitrile

HRID 1881665Notes

Reaction equation

HRID 1881665 reaction equation
[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([CH:19]=O)=[CH:10][C:11]=3[C:12]2([CH2:17][CH3:18])[CH2:15][CH3:16])=[CH:4][CH:3]=1.Cl.[NH2:22]O>C(O)=O>[Br:1][C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([C:19]#[N:22])=[CH:10][C:11]=3[C:12]2([CH2:17][CH3:18])[CH2:15][CH3:16])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 154763497-Bromo-9,9-diethylfluorene-2-carboxaldehyde

Product 1

HCID 710290647-Bromo-9,9-diethylfluorene-2-carbonitrile

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent

Procedure

An alternate, but less satisfactory synthesis was conducted as follows: A mixture of 7-bromo-9,9-diethylfluorene-2-carboxaldehyde (3.29 g, 10.0 mmol), hydroxylamine hydrochloride (0.9 g, 10.0 mmol), and formic acid (15 mL), was held at reflux for 2 hours, cooled and filtered. The filtrate was worked up by extraction into toluene, washing the extract with water, and bicarbonate solution, drying and concentration. The residue was combined with the formic acid-insoluble solids, and chromatographed over silica gel. There were obtained, the desired nitrile product, 1.58 g (49%), m.p. 85-87° C., mass spectrum (m/z): 325, 327 (M+); the amide byproduct, 0.42 g (12%), m.p. 179-184° C., mass spectrum (m/z): 343, 345 (M+); and the oxime by-product, m.p. 104-107° C., 0.17 g (5%), mass spectrum (m/z): 343 (M+)

Workup

  1. customAn alternate, but less satisfactory synthesis
  2. temperatureat reflux for 2 hours
  3. temperaturecooled
  4. filtrationfiltered
  5. extractionThe filtrate was worked up by extraction into toluene
  6. washwashing the
  7. extractionextract with water, and bicarbonate solution
  8. customdrying
  9. concentrationconcentration
  10. customchromatographed over silica gel
  11. customThere were obtained

Sources & evidence

ORD record
ord-1eb84f29bc42443580ce9528d0986d0f
Source dataset
uspto-grants-2012_11
Patent number
US08318888B1

Reaction notes

Loading…