Menthyl chloroformate → HCID 14850317, compound

HRID 1651127Notes

Reaction equation

HRID 1651127 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[C:18](=[O:19])[CH2:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]2=[O:20])=[C:4]([F:21])[CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].Cl[C:33]([O:35][CH:36]1[CH:41]([CH:42]([CH3:44])[CH3:43])[CH2:40][CH2:39][CH:38]([CH3:45])[CH2:37]1)=[O:34]>C1COCC1>[CH:38]1([CH3:45])[CH2:39][CH2:40][CH:41]([CH:42]([CH3:44])[CH3:43])[CH:36]([O:35][C:33]([CH:17]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10](=[O:20])[N:9]([CH2:8][C:5]3[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][C:4]=3[F:21])[C:18]2=[O:19])=[O:34])[CH2:37]1

Participants

5

Reactant 3

HCID 151928Menthyl chloroformateHCID 2733832Lithium HexamethyldisilazideHCID 10383090HCID 10383090, compound

Product 1

HCID 14850317HCID 14850317, compoundYield 74.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a cold (-78° C.) solution of 2-[(4-bromo-2-fluorophenyl)methyl]-1,3(2H, 3H)-isoquinolinedione (9.0 g, 25.86 mmol) in anhydrous THF (120 mL) was added lithium bis(trimethylsilyl)amide (1.0M solution in THF, 56.91 mL, 56.91 mmol), dropwise over a 10 minute period. After stirring for 3 hours, (-)menthyl chloroformate (8.48 mL, 38.79 mmol) was added and the reaction was allowed to warm up to room temperature. The mixture during that period turned a dark color. It was stirred an additional 30 minutes and quenched with H2O. The dark solution was poured into H2O, acidified with HCl (2N) and extracted with EtOAc. The organic extracts were dried over MgSO4. Evaporation and purification by flash chromatography on acid-washed silica gel (5% H3PO4 in MeOH) gave a clear oil (10.2 g).

Workup

  1. waitThe mixture during that period turned
  2. stirringIt was stirred an additional 30 minutes
  3. customquenched with H2O
  4. additionThe dark solution was poured into H2O
  5. extractionextracted with EtOAc
  6. dry with materialThe organic extracts were dried over MgSO4
  7. customEvaporation and purification by flash chromatography
  8. washon acid-washed silica gel (5% H3PO4 in MeOH)

Sources & evidence

ORD record
ord-ab1c15b63a9b41ffa9018621958846c0
Source dataset
uspto-grants-1990_05
Patent number
US04927831

Reaction notes

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