Diisopropylamine → HCID 67478666, compound

HRID 1027398Notes

Reaction equation

HRID 1027398 reaction equation
C(N[CH:5]([CH3:7])[CH3:6])(C)C.C([Li])CCC.CCCCCC.[CH2:19]([O:21][C:22]([CH:24]1[CH2:29][CH2:28][CH:27]([O:30][Si:31]([C:44]([CH3:47])([CH3:46])[CH3:45])([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH2:26][CH2:25]1)=[O:23])[CH3:20].C(I)C=C>C1COCC1.CN(C)P(N(C)C)(N(C)C)=O>[CH2:19]([O:21][C:22]([C:24]1([CH2:7][CH:5]=[CH2:6])[CH2:29][CH2:28][CH:27]([O:30][Si:31]([C:44]([CH3:45])([CH3:47])[CH3:46])([C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[CH2:26][CH2:25]1)=[O:23])[CH3:20]

Participants

8

Reactant 5

HCID 7912DiisopropylamineHCID 8058HexaneHCID 11166Allyl iodideHCID 58018637HCID 58018637, compoundHCID 178418339Butyllithium

Product 1

HCID 67478666HCID 67478666, compoundYield 99%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-78 °C

Procedure

Diisopropylamine (3.14 g, 4.38 mL, 31 mmol) was dissolved in THF (100 mL) and cooled to −78° C. To this solution was added 2.5 M n-butyl lithium in hexane (12.4 mL, 31 mmol) and stirred for 15 min, warmed up to 0° C. and stirred for an additional min, then re-cooled to −78° C. 4-(tert-Butyl-diphenyl-silanyloxy)-cyclohexanecarboxylic acid ethyl ester (10.5 g, 25.6 mmol) in THF (15 mL) was then added and the reaction mixture was allowed to stir at −78° C. for 1 h followed by the addition of a mixture of hexamethyl-phosphoramide (HMPA) (7 mL) and allyl iodide (5.59 g, 33.3.0 mmol). This mixture was stirred at −78° C. for 20 min. Then, the dry ice bath was removed and the stirring was continued to allow the reaction mixture to warm to room temperature over 1 h. The reaction mixture was poured into ice-water (100 mL) and ether (50 mL). The two layers were separated; the aqueous layer was extracted with ether (3×50 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated under vacuum to afford 11.4 g (99%) of the title compound.

Workup

  1. temperaturewarmed up to 0° C.
  2. stirringstirred for an additional min
  3. temperaturere-cooled to −78° C
  4. stirringto stir at −78° C. for 1 h
  5. stirringThis mixture was stirred at −78° C. for 20 min
  6. customThen, the dry ice bath was removed
  7. temperatureto warm to room temperature over 1 h
  8. additionThe reaction mixture was poured into ice-water (100 mL) and ether (50 mL)
  9. customThe two layers were separated
  10. extractionthe aqueous layer was extracted with ether (3×50 mL)
  11. washThe combined organic layers were washed with brine
  12. dry with materialdried over Na2SO4
  13. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-cfb9d4ba644a472a9cc4140f21f6be57
Source dataset
uspto-grants-2014_05
Patent number
US08735385B2

Reaction notes

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