1,1-Dichloroethane → HCID 66906414, compound

HRID 1690623Notes

Reaction equation

HRID 1690623 reaction equation
C[Li].[CH3:3][Si](Cl)(C)C.[CH3:8][O:9][CH2:10][CH2:11][CH2:12][O:13][C:14]1[CH:15]=[C:16]([C:31]([CH3:38])=[CH:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:17]=[CH:18][C:19]=1[O:20][Si:21]([CH:28]([CH3:30])[CH3:29])([CH:25]([CH3:27])[CH3:26])[CH:22]([CH3:24])[CH3:23].ClC(Cl)C.[Cl-].[NH4+]>C(OCC)C.[Cu]I>[CH3:8][O:9][CH2:10][CH2:11][CH2:12][O:13][C:14]1[CH:15]=[C:16]([C:31]([CH3:3])([CH3:38])[CH2:32][C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:17]=[CH:18][C:19]=1[O:20][Si:21]([CH:28]([CH3:29])[CH3:30])([CH:22]([CH3:23])[CH3:24])[CH:25]([CH3:27])[CH3:26]

Participants

8

Reactant 5

HCID 63651,1-DichloroethaneHCID 6397ChlorotrimethylsilaneHCID 25517Ammonium ChlorideHCID 66906859HCID 66906859, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 66906414HCID 66906414, compoundYield 103.2%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

At 0° C., copper (I) iodide (4.11 g, 21.6 mmol) was dissolved in diethyl ether (10 mL). Methyllithium (1.6N, 27 mL) was added and the mixture was stirred for 10 minutes. The solvent was removed under reduced pressure and cold dichloromethane (10 mL) was added. The solvent was removed under reduced pressure. Cold dichloroethane (83 mL) was added and the mixture was cooled to −78° C. Trimethylsilyl chloride (2.73 mL, 21.6 mmol) was added, followed by a solution of ethyl 3-{3-(3-methoxypropoxy)-4-[(triisopropylsilyl)oxy]phenyl}but-2-enoate (2.43 g, 5.4 mmol) and dichloroethane (10 mL). The temperature was maintained at 0° C. for 3 hrs and the mixture was then hydrolyzed with saturated aqueous ammonium chloride. The aqueous layer was extracted with dichloromethane. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate, 95/5) to yield 2.6 g (84%) of the desired product as an oil.

Workup

  1. customThe solvent was removed under reduced pressure and cold dichloromethane (10 mL)
  2. additionwas added
  3. customThe solvent was removed under reduced pressure
  4. additionCold dichloroethane (83 mL) was added
  5. temperatureThe temperature was maintained at 0° C. for 3 hrs
  6. extractionThe aqueous layer was extracted with dichloromethane
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate, 95/5)

Sources & evidence

ORD record
ord-ede0fe18954f424aac7434101a3f4c89
Source dataset
uspto-grants-2012_04
Patent number
US08153647B2

Reaction notes

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