Cesium carbonate → Methyl 2-(6-chloro-5-iodo-1H-benzo[d]imidazol-2-ylthio)acetate

HRID 2193845Notes

Reaction equation

HRID 2193845 reaction equation
[Cl:1][C:2]1[C:11]([I:12])=[CH:10][C:5]2[NH:6][C:7](=[S:9])[NH:8][C:4]=2[CH:3]=1.Br[CH2:14][C:15]([O:17][CH3:18])=[O:16].C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1>[Cl:1][C:2]1[C:11]([I:12])=[CH:10][C:5]2[N:6]=[C:7]([S:9][CH2:14][C:15]([O:17][CH3:18])=[O:16])[NH:8][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 60984Methyl bromoacetateHCID 574814685-Chloro-6-iodo-1H-benzo[d]imidazole-2(3H)-thione2×

Product 1

HCID 58387206Methyl 2-(6-chloro-5-iodo-1H-benzo[d]imidazol-2-ylthio)acetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 6-chloro-5-iodo-2-thio-1H-benzo[d]imidazole (Intermediate 7; 4.00 g, 12.9 mmol), methyl bromoacetate (1.2 mL, 12.9 mmol), and Cs2CO3 (8.41 g, 25.8 mmol) in 65 mL of THF was stirred for 2.5 h at rt. The volume of the solvent was reduced by rotary evaporation to about 20 mL, the mixture was diluted with 200 mL of EtOAc and washed with brine, dried (MgSO4) and evaporated. The resulting residue was subjected to chromatography on an 80 g column of SiO2 eluting with 14% EtOAc in hexanes, followed by 20% to provide the title compound as an amorphous solid, which exists as a tautomer mixture in DMSO according to 1H NMR: 1H NMR (500 MHz, DMSO-d6): δ 3.66, 3.72, 3.73 (s each, 3H), 4.24, 4.25, 4.26 (s each, 2H), 7.71, 7.95 (s each, 1H), 7.99, 8.11, 8.22 (s each, 1H), 12.91 (br s, 1H); LC-MS: calculated for C10H8ClIN2O2S 382.6, observed m/e 382.9/384.9 (M+H)+.

Workup

  1. customThe volume of the solvent was reduced by rotary evaporation to about 20 mL
  2. additionthe mixture was diluted with 200 mL of EtOAc
  3. washwashed with brine
  4. dry with materialdried (MgSO4)
  5. customevaporated

Sources & evidence

ORD record
ord-2507ce8d653645888827c160d6dd5dff
Source dataset
uspto-grants-2012_12
Patent number
US08329914B2

Reaction notes

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