Chloromethyl methyl sulfide → 2-Chloro-n-ethyl-n-[(methylthio)methyl]-6-(trimethylsilyl)benzamide

HRID 368681Notes

Reaction equation

HRID 368681 reaction equation
[Cl:1][C:2]1[CH:12]=[CH:11][CH:10]=[C:9]([Si:13]([CH3:16])([CH3:15])[CH3:14])[C:3]=1[C:4]([NH:6][CH2:7][CH3:8])=[O:5].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Cl[CH2:28][S:29][CH3:30]>C1COCC1>[Cl:1][C:2]1[CH:12]=[CH:11][CH:10]=[C:9]([Si:13]([CH3:15])([CH3:14])[CH3:16])[C:3]=1[C:4]([N:6]([CH2:7][CH3:8])[CH2:28][S:29][CH3:30])=[O:5]

Participants

5

Reactant 3

HCID 16916Chloromethyl methyl sulfide2×HCID 2724254Sodium bis(trimethylsilyl)amideHCID 186303792-Chloro-n-ethyl-6-(trimethylsilyl)benzamide

Product 1

HCID 186302472-Chloro-n-ethyl-n-[(methylthio)methyl]-6-(trimethylsilyl)benzamideYield 45%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2.0 g (7.8 mmol) of the compound of Example 45 in 30 mL dry THF was added 7.9 mL (7.9 mmol) sodium bis(trimethylsilyl)amide (1.0 M in THF). To the resulting mixture was added 1.0 g (10.4 mmol) chloromethyl methylsulfide. The mixture was stirred for 15 min and another 0.65 g (6.7 mmol) of chloromethyl methylsulfide was added. Stirring at RT was continued for 1 h and the mixture was then heated to reflux for 28 hours. The mixture was allowed to cool to RT and was then partitioned between ether and water. The organic layer was washed with brine, dried (MgSO4), and was filtered through silica gel. The filtrate was evaporated in vacuo and the residue was chromatographed (HPLC, 8% ethyl acetate/hexane) to yield 1.1 g (45%) of a colorless oil. nD25 =1.5526.

Workup

  1. stirringStirring at RT
  2. waitwas continued for 1 h
  3. temperaturethe mixture was then heated
  4. temperatureto reflux for 28 hours
  5. customwas then partitioned between ether and water
  6. washThe organic layer was washed with brine
  7. dry with materialdried (MgSO4)
  8. filtrationwas filtered through silica gel
  9. customThe filtrate was evaporated in vacuo
  10. customthe residue was chromatographed (HPLC, 8% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-47c985730dea49e892cae3b3d0cf52f1
Source dataset
uspto-grants-2000_10
Patent number
US06133252

Reaction notes

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