Sodium Carbonate → 4-Nitrophenyl 2-chloro-3-fluorobenzylcarbamate

HRID 340894Notes

Reaction equation

HRID 340894 reaction equation
[CH:1]1[C:6]([N+:7]([O-:9])=[O:8])=[CH:5][CH:4]=[C:3]([Cl-]C([O-])=O)[CH:2]=1.[Cl:14][C:15]1[C:22]([F:23])=[CH:21][CH:20]=[CH:19][C:16]=1[CH2:17][NH2:18].[C:24](=O)([O-:26])[O-:25].[Na+].[Na+]>C(Cl)Cl>[Cl:14][C:15]1[C:22]([F:23])=[CH:21][CH:20]=[CH:19][C:16]=1[CH2:17][NH:18][C:24](=[O:25])[O:26][C:3]1[CH:2]=[CH:1][C:6]([N+:7]([O-:9])=[O:8])=[CH:5][CH:4]=1

Participants

4

Reactant 2

HCID 10340Sodium CarbonateHCID 50998690(2-Chloro-3-fluorophenyl)methanamine

Product 1

HCID 579475384-Nitrophenyl 2-chloro-3-fluorobenzylcarbamate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A 5 liter 3-neck RBF was charged with 4-nitrophenylchloroformate (126.3 g, 627 mmol), DCM (3000 mL), under N2 atm and chilled in a 0° C. ice bath. A solution of 2-chloro,3-fluorobenzylamine (100.0 g, 627 mmol) followed by solid Sodium Carbonate (155.0 g, 1460 mmol) was quickly added in one portion into the reaction solution. The reaction mixture was stirred at 0° C. for 1 h and an LC/MS was taken to confirm consumption of the starting material and presence of the nitrophenyl intermediate. The reaction mixture was allowed to warm to room temperature and stirred for approximately 2 h. The mixture was filtered, and the filtrate was concentrated to give a white solid. The solid was redissolved with 600 ml of DCM and heated to 40° C. until all of the material went into solution. The solution was chilled in a 0° C. ice bath to form crystals. The crystals were collected and dried under vacuum to give 4-nitrophenyl 2-chloro-3-fluorobenzylcarbamate. (150 g, 75%).

Workup

  1. additionwas quickly added in one portion into the reaction solution
  2. customconsumption of the starting material and presence of the nitrophenyl intermediate
  3. temperatureto warm to room temperature
  4. stirringstirred for approximately 2 h
  5. filtrationThe mixture was filtered
  6. concentrationthe filtrate was concentrated
  7. customto give a white solid
  8. temperatureheated to 40° C. until all of the material
  9. temperatureThe solution was chilled in a 0° C. ice bath
  10. customto form crystals
  11. customThe crystals were collected
  12. customdried under vacuum

Sources & evidence

ORD record
ord-0cd58189bae04e9bbca50511f77924a8
Source dataset
uspto-grants-2014_11
Patent number
US08895582B2

Reaction notes

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