Potassium Iodide → 9,9-Diethyl-7-iodofluorene-2-carboxaldehyde

HRID 380189Notes

Reaction equation

HRID 380189 reaction equation
[CH2:1]([C:3]1([CH2:19][CH3:20])[C:15]2[CH:14]=[C:13]([CH:16]=[O:17])[CH:12]=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][C:6](Br)=[CH:7][CH:8]=2)[CH3:2].C(P(CCCC)CCCC)CCC.[I-:34].[K+].CN(C=O)C>C1(C)C=CC=CC=1.[Ni](Br)Br>[CH2:1]([C:3]1([CH2:19][CH3:20])[C:15]2[CH:14]=[C:13]([CH:16]=[O:17])[CH:12]=[CH:11][C:10]=2[C:9]2[C:4]1=[CH:5][C:6]([I:34])=[CH:7][CH:8]=2)[CH3:2]

Participants

7

Reactant 4

HCID 4875Potassium IodideHCID 6228DimethylformamideHCID 13831TributylphosphineHCID 154763497-Bromo-9,9-diethylfluorene-2-carboxaldehyde

Product 1

HCID 183689219,9-Diethyl-7-iodofluorene-2-carboxaldehydeYield 75%

Reagents, catalysts & solvents 2

HCID 278492Nickel(II) bromideCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 9,9-diethyl-7-bromofluorene-2-carboxaldehyde, (28.8 g., 0.0875 mol.), nickel (II) bromide (2.1 g., 9.6 mmol.), tri-n-butyl phosphine (4m1, 16 mmol.), potassium iodide (52.0 g., 0.3132 mole, 3.6 equivalents), and DMF (125 ml), was held at reflux under an atmosphere of nitrogen for 15 hours, cooled, diluted with toluene (450 ml), and filtered. The filtrate was washed with water in several portions, dried, and concentrated. The residual solids were recrystallized from toluene-heptane (1:2, 150 ml); 24.79 g., m.p. 138-140° C., (75% yield). When the reaction was run longer, 24 and 34 hours, the yields fell to 61 and 59% respectively. Mass Spec (m/z): 376 (M+), not contaminated with the bromo aldehyde. Anal.Calcd. for C18H17Ol: C, 57.46; H, 4.55; and l, 33.73%. Found: C, 58.04 and 58.02; H, 4.72 and 4.66; and l, 32.62 and 32.89.

Workup

  1. temperatureat reflux under an atmosphere of nitrogen for 15 hours
  2. temperaturecooled
  3. filtrationfiltered
  4. washThe filtrate was washed with water in several portions
  5. customdried
  6. concentrationconcentrated
  7. customThe residual solids were recrystallized from toluene-heptane (1:2, 150 ml)
  8. custom24 and 34 hours

Sources & evidence

ORD record
ord-3d180c16ac664feaa26e72325d6d731b
Source dataset
uspto-grants-2001_10
Patent number
US06300502B1

Reaction notes

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