Diisopropylamine → HCID 20130467, compound

HRID 846005Notes

Reaction equation

HRID 846005 reaction equation
C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.C(=O)=O.CC(C)=O.[C:28]1([CH:34]2[CH:39]([C:40]([O:42][CH2:43][CH3:44])=[O:41])[CH2:38][CH:37]=[CH:36][CH2:35]2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.[Cl:45][CH2:46][CH2:47][CH2:48]I>O1CCCC1.O>[CH2:43]([O:42][C:40]([C:39]1([CH2:48][CH2:47][CH2:46][Cl:45])[CH:34]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH2:35][CH:36]=[CH:37][CH2:38]1)=[O:41])[CH3:44]

Participants

9

Reactant 6

HCID 7912DiisopropylamineHCID 813631-Chloro-3-iodopropaneHCID 2724682Lithium diisopropylamideHCID 18522661Acetone cardiceHCID 20130457HCID 20130457, compoundHCID 178418339Butyllithium

Product 1

HCID 20130467HCID 20130467, compoundYield 77%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of lithium diisopropylamide (LDA), prepared at 0° C. under a nitrogen (N2) atmosphere from diisopropylamine (0.311 mol, 31.4 g) and n-butyllithium (0.311 mol, 2.7M, 115.3 ml) using tetrahydrofuran (400 ml) as solvent, was cooled to -78° C. employing a dry ice/acetone slurry. Ethyl 6-phenyl-3-cyclohexene-1-carboxylate (0.283 mol, 65 g) dissolved in tetrahydrofuran (100 ml) was added to the solution. After 45 min., 1-chloro-3-iodopropane (0.311 mol, 63.5 g) dissolved in tetrahydrofuran (50 ml) was added dropwise over the period of 30 min. The contents were allowed to warm to room temperature, whereupon 300 ml of water is added and the mixture was extracted three times with 200 ml of ethyl ether. The combined organic extracts were washed with 10% aqueous sodium thiosulfate and brine and dried over magnesium sulfate (MgSO4). Upon filtration, the filtrate was concentrated in vacuo to afford a yellow oil which is distilled (155°-160° C./0.05 mm) to afford ethyl-1-(3-chloropropyl)-6-phenyl-3-cyclohexene-1-carboxylate (66.75 g, 77% yield).

Workup

  1. additionwas added to the solution
  2. additionwas added dropwise over the period of 30 min
  3. additionis added
  4. extractionthe mixture was extracted three times with 200 ml of ethyl ether
  5. washThe combined organic extracts were washed with 10% aqueous sodium thiosulfate and brine
  6. dry with materialdried over magnesium sulfate (MgSO4)
  7. filtrationUpon filtration
  8. concentrationthe filtrate was concentrated in vacuo
  9. customto afford a yellow oil which
  10. distillationis distilled (155°-160° C./0.05 mm)

Sources & evidence

ORD record
ord-e5029da8e4644fa9b3d481e826cc592e
Source dataset
uspto-grants-1988_07
Patent number
US04760146

Reaction notes

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