Methyl iodide → Methyl 5-phenyl-thiophene-2-carbodithioate

HRID 2298382Notes

Reaction equation

HRID 2298382 reaction equation
[Li]CCCC.[C:6]1([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[Br-].[Li+].[C:19](=[S:21])=[S:20].I[CH3:23]>C1COCC1.[Cu]Br>[C:6]1([C:12]2[S:13][C:14]([C:19]([S:21][CH3:23])=[S:20])=[CH:15][CH:16]=2)[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

8

Reactant 5

HCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 699992-PhenylthiopheneHCID 82050Lithium BromideHCID 178418339Butyllithium

Product 1

HCID 18337421Methyl 5-phenyl-thiophene-2-carbodithioateYield 99.8%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a cooled (−10 to 0° C.) solution of n-BuLi (22.7 mL, 33.4 mmol) in THF (10 mL) is added dropwise a solution of 2-phenyl-thiophene (5.46 g, 34.0 mmol) in THF (15 mL). The resulting green solution is stirred at 0° C. After 30 minutes, a solution of copper (I) bromide (0.87 g, 6.1 mmol) and lithium bromide (1.29 g, 14.9 mmol) in TBF (20 mL) is added to the cooled reaction solution over several minutes. The resulting dark green solution is stirred at 0° C. for 15 minutes, at Which time, carbon disulfide (2.0 mL, 34.0 mmol) is added dropwise over 15 minutes. The resulting dark brown solution is stiffed for 30 minutes, then iodomethane (2.9 mL, 46.4 mmol) is added dropwise to the reaction solution over 5 minutes. The resulting dark brown solution is allowed to warm to room temperature and stirred for 1 hour, then is quenched with a solution of potassium cyanide in water (100 mL). The biphasic mixture was diluted with EtOAc and washed with brine, dried over MgSO4, filtered, and concentrated to give a dark orange solid (8.5 grams) which is purified with flash chromatography on silica gel (eluent: gradient of heptane to 2% THF/heptane) to give an orange solid. Yield 34%. HRMS (FAB) calculated for C12H10S3+H 251.0023, found 251.0023.

Workup

  1. additionis added dropwise over 15 minutes
  2. waitThe resulting dark brown solution is stiffed for 30 minutes
  3. temperatureto warm to room temperature
  4. stirringstirred for 1 hour
  5. customis quenched with a solution of potassium cyanide in water (100 mL)
  6. additionThe biphasic mixture was diluted with EtOAc
  7. washwashed with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-133e517018bd409cbbfaf004237e5243
Source dataset
uspto-grants-2002_12
Patent number
US06492385B2

Reaction notes

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