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

HRID 1045094Notes

Reaction equation

HRID 1045094 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 2; 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-f839f2ee30f84feead8f92a432ea34d6
Source dataset
uspto-grants-2013_10
Patent number
US08563746B2

Reaction notes

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