Iodine → HCID 60797754, compound

HRID 222197Notes

Reaction equation

HRID 222197 reaction equation
[Mg].CCOCC.II.[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16]Cl)=[CH:12][CH:11]=1.[CH:18](=[O:22])[CH:19]([CH3:21])[CH3:20]>>[Cl:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][CH:18]([OH:22])[CH:19]([CH3:21])[CH3:20])=[CH:12][CH:11]=1

Participants

6

Reactant 5

HCID 807IodineHCID 3283Diethyl Ether3×HCID 6561IsobutyraldehydeHCID 77231-Chloro-4-(chloromethyl)benzeneHCID 5462224Magnesium

Product 1

HCID 60797754HCID 60797754, compound

Conditions

Temperature
45 °C

Procedure

Magnesium (5.02 g, 0.206 mol) was covered in dry ether (50 mL, 0.5 mol) under an atmosphere of nitrogen. Iodine (0.254 g, 0.001 mol) was added to the reaction, followed by approximately 1 mL of a solution of 1-chloro-4-(chloromethyl)-benzene (32.20 g, 0.200 mol) in ether (25.0 mL, 0.238 mol). An exotherm was noted and the mixture reached reflux. The slow addition of solution was continued over 90 minutes to maintain a gentle reflux. On completion of the addition, the reaction was heated for 30 minutes at 45° C. The reaction was then cooled to 0° C. Isobutyraldehyde (25.19 mL, 0.2774 mol) in Ether (20 mL, 0.2 mol) was then added slowly over 2 hours at 0° C. On completion of the addition the reaction was allowed to warm to room temperature and stir overnight. The reaction was then quenched with ice (200 g) and acidified with 2M HCl (100 mL). The organic phase was separated and the aqueous was extracted twice with more ether. The combined organic phase was evaporated and the residue was purified by silica gel chromatography, eluting with 0 to 10% methanol in dichloromethane to yield the product, 17.8 g (45%). 1H NMR (300 MHz, CDCl3, δ): 7.22 (m, 4H), 3.56 (m, 1H), 2.81 (dd, J=3.3 Hz, 13.7 Hz, 1H), 2.58 (dd, J=9.4 Hz, 13.7 Hz, 1H), 1.74 (dt, J=6.5 Hz, 12.9 Hz, 1H), 1.45 (s, 1H), 1.00 (s, 3H), 0.98 (s, 3H).

Workup

  1. temperaturethe mixture reached reflux
  2. additionThe slow addition of solution
  3. temperatureto maintain a gentle reflux
  4. additionOn completion of the addition
  5. temperatureThe reaction was then cooled to 0° C
  6. additionOn completion of the addition the reaction
  7. temperatureto warm to room temperature
  8. customThe reaction was then quenched with ice (200 g)
  9. customThe organic phase was separated
  10. extractionthe aqueous was extracted twice with more ether
  11. customThe combined organic phase was evaporated
  12. customthe residue was purified by silica gel chromatography
  13. washeluting with 0 to 10% methanol in dichloromethane
  14. customto yield the product, 17.8 g (45%)

Sources & evidence

ORD record
ord-fc804ed6b1cd441898ac4c27bb105a97
Source dataset
uspto-grants-2012_06
Patent number
US08207177B2

Reaction notes

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