Dimethyl Disulfide → Dimethyl-(5-methylsulfanyl-2-triisopropylsilanyl-2,7,8,9-tetrahydro-6-oxa-2-azabenzo[cd]-azulen-8-yl)amine

HRID 25338

Reaction equation

HRID 25338 reaction equation
Br[C:2]1[O:11][CH2:10][C:9]2[CH:8]([N:12]([CH3:14])[CH3:13])[CH2:7][C:6]3=[CH:15][N:16]([Si:18]([CH:25]([CH3:27])[CH3:26])([CH:22]([CH3:24])[CH3:23])[CH:19]([CH3:21])[CH3:20])[CH:17]=[C:4]([C:5]=23)[CH:3]=1.[Li]CCCC.[CH3:33][S:34]SC>O1CCCC1.[Cl-].[NH4+]>[CH3:14][N:12]([CH3:13])[CH:8]1[C:9]2[CH2:10][O:11][C:2]([S:34][CH3:33])=[CH:3][C:4]3=[CH:17][N:16]([Si:18]([CH:22]([CH3:24])[CH3:23])([CH:25]([CH3:27])[CH3:26])[CH:19]([CH3:20])[CH3:21])[CH:15]=[C:6]([C:5]=23)[CH2:7]1

Participants

6

Reactant 3

HCID 12232Dimethyl DisulfideHCID 69736345(5-Bromo-2-triisopropylsilanyl-2,7,8,9-tetrahydro-6-oxa-2-azabenzo[cd]azulen-8-yl)dimethylamineHCID 178418339Butyllithium

Product 1

HCID 69736433Dimethyl-(5-methylsulfanyl-2-triisopropylsilanyl-2,7,8,9-tetrahydro-6-oxa-2-azabenzo[cd]-azulen-8-yl)amineYield 69%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 25517Ammonium ChlorideSolvent

Procedure

A solution of compound (42) 451 mg in dry tetrahydrofuran 5 ml was cooled at −70° C. n-BuLi (1.56 mol/l hexane solution) 1.3 ml was added dropwise to the solution and the mixture was stirred for 1 h. Then, dimethyldisulfide 185 μl was added and the mixture was stirred for 2 h. The reaction mixtures was diluted with an aqueous ammonium chloride solution and extracted with ethyl acetate. The extracts were washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue obtained was chromatographed on aluminum oxide in ethyl acetate:hexane (1:5) to give the titled compound as colorless crystals, 289.8 mg. Yield 69%. This was recrystallized from hexane to give the titled compound as colorless crystals, m.p. 77-79° C.

Workup

  1. additionwas added dropwise to the solution
  2. stirringthe mixture was stirred for 2 h
  3. customThe reaction mixtures
  4. extractionextracted with ethyl acetate
  5. washThe extracts were washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe residue obtained
  9. customwas chromatographed on aluminum oxide in ethyl acetate:hexane (1:5)

Sources & evidence

ORD record
ord-88856aa7067d48b783d67b38e16f531d
Source dataset
uspto-grants-2005_02
Patent number
US06858640B2

Linked notes

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