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

HRID 1028330Notes

Reaction equation

HRID 1028330 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 concentrating. The residue was combined with the formic acid-insoluble solids and chromatographed over silica gel. Obtained were the desired nitrile product, 1.58 g (49%), m.p. 85-87° C., mass spec (m/z): 325, 327 (M+); the amide byproduct, 0.42 g (12%), m.p. 179-184° C., mass spec (m/z): 343, 345 (M+); and the oxime byproduct, m.p. 104-107° C., 0.17 g (5%), mass spec (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. concentrationconcentrating
  10. customchromatographed over silica gel
  11. customObtained

Sources & evidence

ORD record
ord-0f6c7b919b304f79b803bba883067a1a
Source dataset
uspto-grants-2014_05
Patent number
US08735528B1

Reaction notes

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