Di-tert-butyl dicarbonate → HCID 86708481, compound

HRID 921607Notes

Reaction equation

HRID 921607 reaction equation
N1C=CN=C1C(O)=O.[NH2:9][C:10]1[CH:11]=[C:12]([CH:15]=[C:16]([Br:19])[C:17]=1[Cl:18])[C:13]#[N:14].[O:20](C(OC(C)(C)C)=O)[C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=O>C(Cl)Cl.CN(C1C=CN=CC=1)C>[Br:19][C:16]1[C:17]([Cl:18])=[C:10]([NH:9][C:21](=[O:20])[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])[CH:11]=[C:12]([C:13]#[N:14])[CH:15]=1

Participants

6

Reactant 3

HCID 90495Di-tert-butyl dicarbonateHCID 5743211H-Imidazole-2-carboxylic acidHCID 867084563-Amino-5-bromo-4-chlorobenzonitrile

Product 1

HCID 86708481HCID 86708481, compoundYield 52.9%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

(I1D): A mixture of 3-bromo-4-chloro-5-nitrobenzonitrile (0.99 g, 3.79 mmol), iron (1.057 g, 18.93 mmol) and ammonium chloride (2.025 g, 37.9 mmol) in THF, MeOH and water (60 ml, 1:1:1) was heated to reflux for 1 h. More iron (0.5 g) and NH4Cl (2 g) added, heated for another 2 h and then cooled to room temperature. Filtered off solid, the filtrate was concentrated to remove the organic solvent. The residue was diluted with water, extracted with EtOAc twice, dried and concentrated to dryness. The resulting solid was trituard with EtOAc, solid was filtered off through celite pad and the filtrate was concentrated to give 0.88 g of 3-amino-5-bromo-4-chlorobenzonitrile as yellow solid which was used as such in the next reaction. Intermediate 1: To a solution of 3-amino-5-bromo-4-chlorobenzonitrile (0.88 g, 3.80 mmol) in DCM (25 mL) was added TEA (1.590 mL, 11.41 mmol), BOC2O (1.059 mL, 4.56 mmol) and DMAP (0.464 g, 3.80 mmol). The mixture was stirred at room temperature for 16 h. The reaction mixture was concentrated, the crude product was purified using ISCO silica gel column (24 g, EtOAc/hexane=0-30%) to give 0.667 g of tert-butyl 3-bromo-2-chloro-5-cyanophenylcarbamate as white solid

Workup

  1. customsuch in the next reaction
  2. concentrationThe reaction mixture was concentrated
  3. customthe crude product was purified

Sources & evidence

ORD record
ord-266cbfa37de14727af0ad7e1b36040b6
Source dataset
uspto-grants-2016_03
Patent number
US09273057B2

Reaction notes

Loading…