Fluorene → HCID 86616340, compound

HRID 2241076Notes

Reaction equation

HRID 2241076 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[CH:6]1C2CC3C(=CC=CC=3)C=2C=CC=1.O1C(CCCCC=C)C1.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.CC1C[C:43]2[S:44][C:45]3[CH:50]=[CH:49][CH:48]=[CH:47][C:46]=3[C:42]=2[CH:41]=1.CC1CC2C3C=CC=CC=3SC=2C=1.C1(C)C=CC(S(O[CH2:75][CH:76]([CH:83]2[C:95]3[CH:94]=[CH:93][CH:92]=[CH:91][C:90]=3[C:89]3[C:84]2=[CH:85][CH:86]=[CH:87][CH:88]=3)[CH2:77][CH2:78][CH2:79][CH2:80]C=C)(=O)=O)=CC=1>C(OCC)C>[CH3:4][C:3]1[C:43]2[S:44][C:45]3[CH:50]=[CH:49][CH:48]=[CH:47][C:46]=3[C:42]=2[CH2:41][C:2]=1[C:1]([CH2:80][CH2:79][CH2:78][CH2:77][CH:76]([CH:83]1[C:84]2[CH:85]=[CH:86][CH:87]=[CH:88][C:89]=2[C:90]2[C:95]1=[CH:94][CH:93]=[CH:92][CH:91]=2)[CH3:75])=[CH2:6]

Participants

8

Reactant 6

HCID 6853FluoreneHCID 73974-Toluenesulfonyl chlorideHCID 296782-(Hex-5-en-1-yl)oxiraneHCID 86616341HCID 86616341, compoundHCID 86616342HCID 86616342, compoundHCID 178418339Butyllithium2×

Product 1

HCID 86616340HCID 86616340, compoundYield 17.5%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) were added dropwise to a solution of 6.64 g (40 mmol) of fluorene in 80 ml of diethyl ether at room temperature and the reaction mixture was stirred for another hour. A solution of 4.8 g (38 mmol) of 1,2-epoxy-7-octene in 20 ml of diethyl ether was then slowly added thereto. After the reaction mixture had been stirred for another hour, 7.6 g (40 mmol) of p-toluenesulfonyl chloride was slowly added as a solid. Separately from this first reaction mixture, a solution of a mixture of 7.4 g (40 mmol) of 2-methyl-3H-cyclopenta[b][1]benzothiophene/2-methyl-1H-cyclopenta[b][1]benzothiophene in 70 ml of diethyl ether was admixed with 16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) and the mixture was stirred for another hour. The second reaction mixture was added dropwise to the first reaction mixture comprising 2-(9H-fluoren-9-yl)oct-7-enyl p-toluenesulfonate, the resulting mixture was stirred for 18 hours and subsequently subjected to an aqueous work-up. After phase separation, the organic phase was washed with water, dried over magnesium sulfate and the solvent was removed under reduced pressure. This gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9). This gave 3.07 g of (1a) (yield 17.5%) as a viscous yellow oil.

Workup

  1. stirringAfter the reaction mixture had been stirred for another hour
  2. stirringthe mixture was stirred for another hour
  3. customThe second reaction mixture
  4. stirringthe resulting mixture was stirred for 18 hours
  5. customAfter phase separation
  6. washthe organic phase was washed with water
  7. dry with materialdried over magnesium sulfate
  8. customthe solvent was removed under reduced pressure
  9. customThis gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9)

Sources & evidence

ORD record
ord-57639c54a40b431289535f366f3df679
Source dataset
uspto-grants-2010_05
Patent number
US07723450B2

Reaction notes

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