Hydrochloric Acid → 1-(Hydroxyimino)-3-methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-one

HRID 2376620Notes

Reaction equation

HRID 2376620 reaction equation
[CH3:1][N:2]1[C:8](=[O:9])[CH2:7][C:6]2[CH:10]=[CH:11][CH:12]=[CH:13][C:5]=2[CH2:4][CH2:3]1.[N:14](OCCC(C)C)=[O:15].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.Cl>C1COCC1>[OH:15][N:14]=[C:7]1[C:6]2[CH:10]=[CH:11][CH:12]=[CH:13][C:5]=2[CH2:4][CH2:3][N:2]([CH3:1])[C:8]1=[O:9]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8053Isoamyl NitriteHCID 8521743-methyl-4,5-dihydro-1H-benzo[d]azepin-2(3H)-oneHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 713578231-(Hydroxyimino)-3-methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-oneYield 85.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a 22 L flask, under nitrogen, was 3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepin-2-one (606 g, 3.46 mol) and isoamyl nitrite (543 g, 4.5 mol) in THF (7.88 L). The mixture was cooled to about 0° C. before LiHMDS (1 N THF solution, 4.5 L, 04.5 mol) was added at a rate such that the temperature remained below about 7° C. After addition, the reaction was allowed to stir at room temperature for about 2 h while monitoring for the reaction progress by HPLC. Upon completion of the reaction, the mixture was cooled to about 0° C., and the pH adjusted from 12 to about 2-1 using aqueous HCl (2N). The resulting precipitate was stirred for about 6 h before isolation by filtration and drying to provide 1-hydroxyimino-3-methyl-2,3,4,5-tetrahydro-1H-3-benzazepin-2-one 604.7 g (85.6%).

Workup

  1. customIn a 22 L flask, under nitrogen, was
  2. additionwas added at a rate such that the temperature
  3. customremained below about 7° C
  4. additionAfter addition
  5. customUpon completion of the reaction
  6. temperaturethe mixture was cooled to about 0° C.
  7. stirringThe resulting precipitate was stirred for about 6 h before isolation by filtration
  8. customdrying

Sources & evidence

ORD record
ord-58e37b2eaeb9407fa9c7c4b75dc3037a
Source dataset
uspto-grants-2008_12
Patent number
US07468365B2

Reaction notes

Loading…