Dimethyl Sulfoxide → 2,7-Dibromo-9-(bis-methylsulfanyl-methylene)fluorene

HRID 496316Notes

Reaction equation

HRID 496316 reaction equation
CC(C)([O-])C.[Na+].[Br:7][C:8]1[CH:20]=[CH:19][C:18]2[C:17]3[C:12](=[CH:13][C:14]([Br:21])=[CH:15][CH:16]=3)[CH2:11][C:10]=2[CH:9]=1.[C:22](=S)=[S:23].CI.[CH3:27][S:28]([CH3:30])=O>>[Br:7][C:8]1[CH:20]=[CH:19][C:18]2[C:17]3[C:12](=[CH:13][C:14]([Br:21])=[CH:15][CH:16]=3)[C:11](=[C:27]([S:23][CH3:22])[S:28][CH3:30])[C:10]=2[CH:9]=1

Participants

6

Reactant 5

HCID 679Dimethyl SulfoxideHCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 1400732,7-DibromofluoreneHCID 23676156Sodium t-butoxide

Product 1

HCID 121516122,7-Dibromo-9-(bis-methylsulfanyl-methylene)fluorene

Procedure

Sodium tert-butoxide (31.1 g, 0.32 mol) was added portionwise over 5 min to a solution of 2,7-dibromofluorene (50 g, 0.154 mol) in DMSO (1000 ml) at RT (22° C.) under nitrogen. To the resulting red solution was added carbon disulfide (13 g, 0.17 mol) via a syringe causing an exotherm to 35° C. The reaction was stirred for 10 min until the internal temperature was 30° C. Methyl iodide (46 g, 0.32 mol) was added over 2 min, causing an exotherm to 42° C. The reaction was stirred for 1 h and quenched by the addition of ice water (1000 ml) and conc. ammonia (20 ml). The reaction was stirred for 10 min and then filtered under reduced pressure and washed with further water (500 ml). After drying the crude yield was 64.8 g (98%, purity (HPLC) 97.8%). Recrystallization from ethyl acetate/THF (2:1) afforded 55.2 g (purity (HPLC) 99.2%).): 1H and 13C NMR spectra as expected; M+=428 (t). Anal. Calcd. For C16H12Br2S2: C, 44.9; H, 2.8, N, 0.0. Found C, 44.7; H, 3.1; N, <0.3.

Workup

  1. customto 35° C
  2. customwas 30° C
  3. customto 42° C
  4. stirringThe reaction was stirred for 1 h
  5. customquenched by the addition of ice water (1000 ml) and conc. ammonia (20 ml)
  6. stirringThe reaction was stirred for 10 min
  7. filtrationfiltered under reduced pressure
  8. washwashed with further water (500 ml)
  9. customAfter drying the crude yield was 64.8 g (98%, purity (HPLC) 97.8%)
  10. customRecrystallization from ethyl acetate/THF (2:1)
  11. customafforded 55.2 g (purity (HPLC) 99.2%)

Sources & evidence

ORD record
ord-a43d9e7930d44d859547aa3af9ced6a8
Source dataset
uspto-grants-2005_09
Patent number
US06943275B2

Reaction notes

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