2-Fluoro-5-iodobenzaldehyde → HCID 68943433, compound

HRID 628620Notes

Reaction equation

HRID 628620 reaction equation
[Br-].[CH3:2][C:3]1[CH:28]=[CH:27][CH:26]=[C:25]([CH3:29])[C:4]=1[CH2:5][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CC(C)([O-])C.[K+].[F:36][C:37]1[C:42]([CH:43]=O)=[CH:41][C:40]([I:45])=[CH:39][CH:38]=1>C(Cl)Cl.C1COCC1>[F:36][C:37]1[CH:38]=[CH:39][C:40]([I:45])=[CH:41][C:42]=1/[CH:43]=[CH:5]/[C:4]1[C:25]([CH3:29])=[CH:26][CH:27]=[CH:28][C:3]=1[CH3:2].[F:36][C:37]1[CH:38]=[CH:39][C:40]([I:45])=[CH:41][C:42]=1/[CH:43]=[CH:5]\[C:4]1[C:25]([CH3:29])=[CH:26][CH:27]=[CH:28][C:3]=1[CH3:2]

Participants

7

Reactant 3

HCID 162170582-Fluoro-5-iodobenzaldehydeHCID 23665647Potassium tert-butoxideHCID 86632151HCID 86632151, compound

Product 2

HCID 68943433HCID 68943433, compoundHCID 68944484HCID 68944484, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 2,6-dimethylbenzyltriphenylphosphonium bromide (2.21 g, 4.8 mmol) in CH2Cl2 (30 mL) was added a solution of potassium tert-butoxide (5 mL of a 1 M solution in THF, 5 mmol) and the mixture was stirred at 0° C. for 15 min. The mixture was cooled to −78° C. and 6-fluoro-3-iodobenzaldehyde (1.0 g, 4.0 mmol) was added. The reaction mixture was allowed to warm to room temperature and stirred overnight. The mixture was partitioned between EtOAc and water and the combined organics were washed with 1 M HCl and brine, dried over Na2SO4 and concentrated under reduced pressure. Purification by flash chromatography (100% hexanes) gave (E)-2-(2-fluoro-5-iodostyryl)-1,3-dimethylbenzene (0.280 g) and (Z)-2-(2-fluoro-5-iodostyryl)-1,3-dimethylbenzene (0.472 g) with additional product collected as an E/Z mixture (0.450 g). Total yield (1.20 g, 85%). Trans-isomer: 1H NMR (400 MHz, DMSO-d6) δ 8.12 (dd, J=7.2, 2.4 Hz, 1H), 7.63 (dq, J=8.8, 2.4 Hz, 1H), 7.34 (d, J=16.8 Hz, 1H), 7.04-7.09 (m, 4H), 6.61 (d, J=16.8 Hz, 1H), 2.30 (s, 6H).

Workup

  1. temperatureThe mixture was cooled to −78° C.
  2. temperatureto warm to room temperature
  3. stirringstirred overnight
  4. customThe mixture was partitioned between EtOAc and water
  5. washthe combined organics were washed with 1 M HCl and brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customPurification by flash chromatography (100% hexanes)

Sources & evidence

ORD record
ord-e17e0f51b6af48308bd34ae27b0310d6
Source dataset
uspto-grants-2016_04
Patent number
US09314467B2

Reaction notes

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