Potassium Hydroxide → Tert-butyl 1-(2-fluorobenzyl)-2-isopropylidenehydrazinecarboxylate

HRID 1973007Notes

Reaction equation

HRID 1973007 reaction equation
[OH-].[K+].[C:3](=[N:6][NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])([CH3:5])[CH3:4].Br[CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[F:23]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[F:23][C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=1[CH2:16][N:7]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[N:6]=[C:3]([CH3:5])[CH3:4]

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 67968alpha-Bromo-o-fluorotolueneHCID 11435207N'-(propan-2-ylidene)(tert-butoxy)carbohydrazide

Product 1

HCID 58529833Tert-butyl 1-(2-fluorobenzyl)-2-isopropylidenehydrazinecarboxylateYield 105.1%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

Powdered KOH (4.24 g, 75.48 mmol) and tetrabutylammonium hydrogen sulfate (1.97 g, 5.81 mmol) were added to a solution of tert-butyl 2-isopropylidenehydrazinecarboxylate (10 g, 58.05 mmol) in toluene (150 mL). The mixture was stirred vigorously and heated to 50° C. and 1-(bromomethyl)-2-fluorobenzene (13.17 g, 69.68 mmol) was added slowly. The temperature was increased to 80° C. and maintained for 3 h and cooled to room temperature. The mixture was washed with water until the pH of the aqueous wash was neutral. The organic layer was washed with brine and dried over MgSO4 and concentrated to give a yellow oil (17.11 g) used for the next step without further purification). LC-MS [M+H]+=280.9, RT=3.41 min.

Workup

  1. temperatureThe temperature was increased to 80° C.
  2. temperaturemaintained for 3 h
  3. temperaturecooled to room temperature
  4. washThe mixture was washed with water until the pH of the
  5. washaqueous wash
  6. washThe organic layer was washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-e2f294fa6ace452888e25804b873d07c
Source dataset
uspto-grants-2013_04
Patent number
US08431695B2

Reaction notes

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