Diethyl Ether → Methyl 6-chloro-2-[2-cyano-2-({[4-(trifluoromethoxy)phenyl]carbonyl}-amino)propyl]-2H-benzotriazole-4-carboxylate

HRID 70966Notes

Reaction equation

HRID 70966 reaction equation
[CH3:1]COCC.C[Si](C=[N+]=[N-])(C)C.[Cl:13][C:14]1[CH:15]=[C:16]([C:42]([OH:44])=[O:43])[C:17]2[C:18]([CH:41]=1)=[N:19][N:20]([CH2:22][C:23]([C:39]#[N:40])([NH:25][C:26]([C:28]1[CH:33]=[CH:32][C:31]([O:34][C:35]([F:38])([F:37])[F:36])=[CH:30][CH:29]=1)=[O:27])[CH3:24])[N:21]=2>C1COCC1.CO>[Cl:13][C:14]1[CH:15]=[C:16]([C:42]([O:44][CH3:1])=[O:43])[C:17]2[C:18]([CH:41]=1)=[N:19][N:20]([CH2:22][C:23]([C:39]#[N:40])([NH:25][C:26]([C:28]1[CH:29]=[CH:30][C:31]([O:34][C:35]([F:37])([F:36])[F:38])=[CH:32][CH:33]=1)=[O:27])[CH3:24])[N:21]=2

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 167693TrimethylsilyldiazomethaneHCID 666203556-chloro-2-[2-cyano-2-({[4-(trifluoromethoxy)phenyl]carbonyl}amino)-propyl]-2H-benzotriazole-4-carboxylic acid

Product 1

HCID 66621025Methyl 6-chloro-2-[2-cyano-2-({[4-(trifluoromethoxy)phenyl]carbonyl}-amino)propyl]-2H-benzotriazole-4-carboxylateYield 40%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A 2 molar ether solution of trimethylsilyldiazomethane was added to 6-chloro-2-[2-cyano-2-({[4-(trifluoromethoxy)phenyl]carbonyl}amino)-propyl]-2H-benzotriazole-4-carboxylic acid (100 mg) dissolved in a ten to 1 one mixture of THF and methanol (2 mL). After overnight at room temperature, the mixture was concentrated under reduced pressure to give a residue that was purified by chromatography (SiO2, heptane/EA) to afford the title compound as a white solid (42 mg, 40%). MS (ES): M/Z [M+H]=482. 1H NMR: (400 MHz, DMSO-d6): 1.75 (s, 3H), 3.78 (s, 3H), 5.44 (d, J=13.3 Hz, 1H), 5.58 (d, J=13.3 Hz, 1H), 7.50 (d, J=8.1 Hz, 2H), 7.92 (d, J=8.8 Hz, 2H), 8.02 (d, J=1.9 Hz, 1H), 8.52 (d, J=1.9 Hz, 1H) and 8.87 (s, 1H). 19F NMR (376 MHz, DMSO-d6): −57.1 (s, 3F).

Workup

  1. concentrationthe mixture was concentrated under reduced pressure
  2. customto give a residue that
  3. customwas purified by chromatography (SiO2, heptane/EA)

Sources & evidence

ORD record
ord-7d7489f663b749439eefdf9985b37639
Source dataset
uspto-grants-2014_09
Patent number
US08822689B2

Reaction notes

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