1-Bromohexane → HCID 22848176, compound

HRID 1656875Notes

Reaction equation

HRID 1656875 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([C@H:15]2[O:20][C:18](=[O:19])[CH2:17][CH2:16]2)=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH3:7].C([N-]C(C)C)(C)C.[Li+].[CH2:29](Br)[CH2:30][CH2:31][CH2:32][CH2:33][CH3:34]>C1(C)C=CC=CC=1.O1CCCC1.CN(C)P(=O)(N(C)C)N(C)C>[CH2:29]([C@H:17]1[CH2:16][C@@H:15]([C:12]2[CH:11]=[CH:10][C:9]([O:8][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH3:7])=[CH:14][CH:13]=2)[O:20][C:18]1=[O:19])[CH2:30][CH2:31][CH2:32][CH2:33][CH3:34]

Participants

7

Reactant 3

HCID 81011-BromohexaneHCID 2724682Lithium diisopropylamideHCID 22848195HCID 22848195, compound

Product 1

HCID 22848176HCID 22848176, compoundYield 1.3%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent3×HCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
-65 °C

Procedure

Rel-(S)-γ-(4-heptyloxyphenyl)-γ-butyrolactone (3.0 g) and anhydrous tetrahydrofuran (50 ml) were placed in a 200 ml three-necked flask, followed by cooling the mixture down to -65° C. with stirring, dropwise adding a tetrahydrofuran solution of lithium diisopropylamide (21.8 mmol) (hereinafter abbreviated to LDA) over 30 minutes, cooling down to -65° C. with stirring for one hour, dropwise adding a mixed solution of hexylbromide (2.71 g), hexamethylphosphoric triamide (hereinafter abbreviated to HMPA) (2.93 g) and anhydrous tetrahydrofuran (5 ml) over 20 minutes, gradually raising the temperature, agitating the mixture at room temperature overnight, adding ice water (50 ml) and toluene (200 ml), washing the resulting organic layer with 2N-hydrochloric acid, saturated NaHCOs aqueous solution and saturated NaCl aqueous solution in this order, drying the organic layer over anhydrous magnesium sulfate, removing magnesium sulfate, concentrating the organic layer under reduced pressure, separation-purifying according to chromatography and recrystallizing from ethanol, to obtain rel-(αS,γS)-α-hexyl-γ-(4-heptyloxyphenyl)-γ-butyrolactone (cis-form) (0.05 g). m.p.: 74.8°-75.8° C.

Workup

  1. temperaturecooling down to -65° C.
  2. stirringwith stirring for one hour
  3. temperaturegradually raising the temperature
  4. stirringagitating the mixture at room temperature overnight
  5. washwashing the resulting organic layer with 2N-hydrochloric acid
  6. dry with materialsaturated NaHCOs aqueous solution and saturated NaCl aqueous solution in this order, drying the organic layer over anhydrous magnesium sulfate
  7. customremoving magnesium sulfate
  8. concentrationconcentrating the organic layer under reduced pressure
  9. customseparation-purifying
  10. customrecrystallizing from ethanol

Sources & evidence

ORD record
ord-5d58cf00e7154e18ab20d1f66cebcf97
Source dataset
uspto-grants-1993_10
Patent number
US05256330

Reaction notes

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