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

HRID 496321Notes

Reaction equation

HRID 496321 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5](=[C:16](SC)SC)[C:4]=2[CH:3]=1.[CH2:21]([Mg]Br)[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32]>C1COCC1.C(OCC)C>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5](=[C:16]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:4][CH2:3][CH2:2][CH2:14][CH3:13])[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[C:4]=2[CH:3]=1

Participants

5

Reactant 2

HCID 121516122,7-Dibromo-9-(bis-methylsulfanyl-methylene)fluoreneHCID 178443215HCID 178443215, compound

Product 1

HCID 121516172,7-Dibromo-9-(bisdodecyl-methylene)fluoreneYield 62%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
2.5 °C

Procedure

To a solution of 2,7-dibromo-9-(bis-methylsulfanyl-methylene)fluorene (4.28, 10 mmol) in dry THF (70 ml) at 0° C. under nitrogen, was added a solution of lithium tetrachlorocuprate (2 ml of a 0.1M solution in THF, 2 mol %). A solution of dodecylmagnesium bromide (22 ml of a 1.0M solution in diethyl ether, 0.022 mol) was added dropwise over 15 min. The reaction was stirred for 3 h at 0-5° C. before quenching with 5% NaOH (100 ml). The reaction was stirred for 10 min and then filtered through celite. The organic layer was separated and the aqueous layer further washed with ethyl acetate (100 ml). The combined organics were washed with brine (100 ml), dried (sodium sulfate), and concentrated under reduced pressure. The crude oil was further purified by filtration through a plug of silica (5 cm×5 cm) covered with a layer of basic alumina (1 cm×5 cm), eluting with petrol. After concentration the residue was recrystallized from isohexane to afford 4.2 of the product as white crystals (62%). Purity (HPLC>98%). 1H and 13C NMR spectra as expected.

Workup

  1. custombefore quenching with 5% NaOH (100 ml)
  2. stirringThe reaction was stirred for 10 min
  3. filtrationfiltered through celite
  4. customThe organic layer was separated
  5. washthe aqueous layer further washed with ethyl acetate (100 ml)
  6. washThe combined organics were washed with brine (100 ml)
  7. dry with materialdried (sodium sulfate)
  8. concentrationconcentrated under reduced pressure
  9. filtrationThe crude oil was further purified by filtration through a plug of silica (5 cm×5 cm)
  10. washeluting with petrol
  11. concentrationAfter concentration the residue
  12. customwas recrystallized from isohexane

Sources & evidence

ORD record
ord-585997a7c7cb49ca877631d8a8a335c1
Source dataset
uspto-grants-2005_09
Patent number
US06943275B2

Reaction notes

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