Dimethyl Sulfoxide → HCID 21885620, compound

HRID 1636036Notes

Reaction equation

HRID 1636036 reaction equation
[Cl:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Cl:15])=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.CS(C)=O.[OH-].[Na+].[CH2:22]([CH:24]([CH2:27][CH2:28][CH2:29][CH3:30])[CH2:25]Br)[CH3:23]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.C(OCC)C.O>[Cl:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Cl:15])=[CH:9][CH:10]=3)[C:5]([CH2:5][CH:4]([CH2:12][CH3:11])[CH2:3][CH2:2][CH2:14][CH3:13])([CH2:25][CH:24]([CH2:22][CH3:23])[CH2:27][CH2:28][CH2:29][CH3:30])[C:4]=2[CH:3]=1

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 14798Sodium HydroxideHCID 868042-Ethylhexyl bromide2×HCID 2519872,7-Dichlorofluorene2×

Product 1

HCID 21885620HCID 21885620, compoundYield 94%

Reagents, catalysts & solvents 3

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Procedure

To a stirred mixture of 2,7-dichlorofluorene (43 g, 0.183 mole) and 120 mL of dimethylsulfoxide (DMSO) under nitrogen is added benzyltriethylammonium chloride (2.3 g, 0.01 mole) and 60 mL of a 50 weight percent aqueous solution of sodium hydroxide. 2-Ethylhexyl bromide (85 g, 0.44 mole) is added and the mixture is agitated well for 2 hours. The reaction is exothermic, the temperature reaching 80° C. within 5 minutes after the addition of 2-ethylhexyl bromide and then falling off to 30° C. over the 2-hour reaction time. Analysis of an aliquot by high pressure liquid chromatography (HPLC) shows the complete disappearance of 2,7-dichlorofluorene and the formation of new product. Water (200 mL), and diethyl ether (250 mL) are added to the reaction mixture, stirred for minutes and the layers are separated. The organic layer is washed with a saturated aqueous NaCl solution, water, dried (MgSO4) and evaporated to remove ether. Fractional vacuum distillation of the residue provides 2,7-dichloro-9,9-di(2-ethylhexyl)-fluorene as clear liquid, boiling point 200° C./1 mm Hg, (79 g, 94 percent yield); HPLC analysis shows that the product is 99 percent pure. Proton Magnetic Spectrum (PMR) analysis is consistent with the title structure.

Workup

  1. waitthe temperature reaching 80° C. within 5 minutes
  2. customfalling off to 30° C. over the 2-hour reaction time
  3. stirringstirred for minutes
  4. customthe layers are separated
  5. washThe organic layer is washed with a saturated aqueous NaCl solution, water
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. customto remove ether
  9. distillationFractional vacuum distillation of the residue

Sources & evidence

ORD record
ord-bad5389e09d2435a8910877c8dfdbc83
Source dataset
uspto-grants-2003_01
Patent number
US06512083B1

Reaction notes

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