Chloromethyl chloroformate → Chloromethyl cyclopropyl(4-methyl-3-nitrobenzoyl)carbamate

HRID 2100364Notes

Reaction equation

HRID 2100364 reaction equation
[CH:1]1([NH:4][C:5](=[O:16])[C:6]2[CH:11]=[CH:10][C:9]([CH3:12])=[C:8]([N+:13]([O-:15])=[O:14])[CH:7]=2)[CH2:3][CH2:2]1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:27](Cl)(=[O:31])[O:28][CH2:29][Cl:30]>C1COCC1>[CH:1]1([N:4]([C:5](=[O:16])[C:6]2[CH:11]=[CH:10][C:9]([CH3:12])=[C:8]([N+:13]([O-:15])=[O:14])[CH:7]=2)[C:27](=[O:31])[O:28][CH2:29][Cl:30])[CH2:3][CH2:2]1

Participants

5

Reactant 3

HCID 62754Chloromethyl chloroformateHCID 2162665N-cyclopropyl-4-methyl-3-nitrobenzamideHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 57799018Chloromethyl cyclopropyl(4-methyl-3-nitrobenzoyl)carbamateYield 72%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of N-cyclopropyl-4-methyl-3-nitrobenzamide (2.10 g, 9.5 mmol) in THF (48 mL) under nitrogen at −78° C. was added lithium bis(trimethylsilyl)amide (1M, THF, 11.4 mL) over 10 min. After 0.5 h, chloromethyl carbonochloridate (1.1 mL, 12.4 mmol) was added. After 10 min., the cold bath was removed, and the reaction was stirred to room temperature for 1.5 h, quenched with water and concentrated in vacuo. It was then diluted with EtOAc and water. After the layers were separated, the organic layer was dried over Na2SO4, filtered, and concentrated in vacuo. Silica gel chromatography using hexanes:EtOAc (5:1) as eluent afforded the title compound as a colorless oil (2.14 g, 72% yield).

Workup

  1. waitAfter 10 min.
  2. customthe cold bath was removed
  3. customquenched with water
  4. concentrationconcentrated in vacuo
  5. additionIt was then diluted with EtOAc and water
  6. customAfter the layers were separated
  7. dry with materialthe organic layer was dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e0ef70a99f6e46048b7a8a363fbde1e9
Source dataset
uspto-grants-2009_08
Patent number
US07572795B2

Reaction notes

Loading…