Iodine → HCID 57656460, compound

HRID 2041468Notes

Reaction equation

HRID 2041468 reaction equation
II.[CH3:3][C:4]([CH3:9])([CH3:8])[CH2:5][CH2:6]Br.[C:10]([C:12]1[CH:19]=[CH:18][C:15]([CH:16]=[O:17])=[CH:14][CH:13]=1)#[N:11]>C1COCC1>[CH3:3][C:4]([CH3:9])([CH3:8])[CH2:5][CH2:6][C:16]([C:15]1[CH:18]=[CH:19][C:12]([C:10]#[N:11])=[CH:13][CH:14]=1)=[O:17]

Participants

5

Reactant 3

HCID 807IodineHCID 660424-CyanobenzaldehydeHCID 1371371-Bromo-3,3-dimethylbutane3×

Product 1

HCID 57656460HCID 57656460, compoundYield 62.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

Keep Mg turnings (402 mg, 15.251 mmol) in vacuo in a two-neck round bottom flask for 2 h. Purge the flask with nitrogen/vacuo several times. Add a couple crystals of iodine, anhydrous THF (60 mL) and 3,3-dimethyl-bromobutane (0.8 mL, 5.59 mmol) slowly (exothermic reaction observed). Add dropwise the remaining 3,3-dimethyl-bromobutane (1.6 mL, 11.18 mmol) and reflux the mixture overnight. Add some additional 3,3-dimethyl-bromobutane (0.24 mL, 1.67 mmol) and reflux for 30 min. Cool the mixture to −10° C. and add a solution of 4-cyanobenzaldehyde (4 g, 30.502 mmol) in anhydrous THF (40 mL). Warm the flask gradually to room temperature overnight. Quench the mixture with 0.1M aqueous HCl (100 mL) and extract twice with EtOAc. Dry the combined organic extracts over Na2SO4, filter and concentrate in vacuo. Purify the crude mixture by chromatography on silica gel eluting with hexane/EtOAc (19:1) to give the desired intermediate as an oil (0.752 g, 23%).

Workup

  1. customfor 2 h
  2. customPurge the flask with nitrogen/vacuo several times
  3. additionAdd
  4. temperaturereflux the mixture overnight
  5. temperaturereflux for 30 min
  6. temperatureWarm the flask gradually to room temperature overnight
  7. customQuench the mixture with 0.1M aqueous HCl (100 mL)
  8. extractionextract twice with EtOAc
  9. dry with materialDry the combined organic extracts over Na2SO4
  10. filtrationfilter
  11. concentrationconcentrate in vacuo
  12. customPurify the crude mixture by chromatography on silica gel eluting with hexane/EtOAc (19:1)

Sources & evidence

ORD record
ord-b129a3ff089c42f98cca5ea341a18a1b
Source dataset
uspto-grants-2013_11
Patent number
US08580780B2

Reaction notes

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