Benzene → 1-tert-butoxycarbonyloxy-6-chloro-1H-benzotriazole

HRID 596216Notes

Reaction equation

HRID 596216 reaction equation
[C:1](Cl)(Cl)=O.[OH:5][N:6]1[C:10]2[CH:11]=[C:12]([Cl:15])[CH:13]=[CH:14][C:9]=2[N:8]=[N:7]1.Cl[C:17]([O:19]N1C2C=C(Cl)C=CC=2N=N1)=[O:18].[CH:30]1[CH:35]=[CH:34]C=CC=1>N1C=CC=CC=1.C(O)(C)(C)C>[C:35]([O:19][C:17]([O:5][N:6]1[C:10]2[CH:11]=[C:12]([Cl:15])[CH:13]=[CH:14][C:9]=2[N:8]=[N:7]1)=[O:18])([CH3:34])([CH3:30])[CH3:1]

Participants

7

Reactant 4

HCID 241Benzene3×HCID 6371PhosgeneHCID 2327116-Chloro-1-hydroxy-1H-benzotriazoleHCID 205679821-chlorocarbonyloxy-6-chloro-1H-benzotriazole

Product 1

HCID 132928521-tert-butoxycarbonyloxy-6-chloro-1H-benzotriazole

Reagents, catalysts & solvents 2

HCID 1049PyridineSolvent2×HCID 6386tert-ButanolSolvent

Procedure

A solution of phosgene (5 g.) in benzene (23.5 ml.) was dropwise added under ice-cooling to a suspension of 1-hydroxy-6-chloro-1H-benzotriazole (8.5 g.) and pyridine (3.9 g.) in benzene (50 ml.), and the mixture was stirred for 30 minutes at the same temperature and allowed to stand overnight. To the resultant solution containing 1-chlorocarbonyloxy-6-chloro-1H-benzotriazole was dropwise added, over 20 minutes under ice-cooling, a solution of tert-butyl alcohol (3.7 g.) and pyridine (4.0 g.) in benzene (50 ml.). The resultant mixture was stirred for 2 hours at the same temperature and allowed to stand overnight. The reaction mixture was filtered, and the filtrate was concentrated. Ether and petroleum ether were added to the residue to pulverize the residue and obtained crystals were collected by filtration to give 1-tert-butoxycarbonyloxy-6-chloro-1H-benzotriazole (5.3 g.). The mother liquor was concentrated to give the same object compound (0.6 g.). Both crystals were put together and dissolved in benzene, after which the solution was washed with a sodium bicarbonate aqueous solution and water and then dried. The solvent was removed by distillation to give the object compound (3.2 g.), powder, mp 98° to 100° C (dec.).

Workup

  1. waitto stand overnight
  2. additionwas dropwise added, over 20 minutes under ice-
  3. temperaturecooling
  4. waitto stand overnight
  5. filtrationThe reaction mixture was filtered
  6. concentrationthe filtrate was concentrated
  7. additionEther and petroleum ether were added to the residue
  8. customobtained crystals
  9. filtrationwere collected by filtration

Sources & evidence

ORD record
ord-1869df57661f4238a3d6a58ae4e3e5fe
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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