Sodium Hydroxide → HCID 66615728, compound

HRID 333579Notes

Reaction equation

HRID 333579 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][C@@H:8]1[C:14]2[C:15]([CH2:17][C@H:18]([CH3:19])[C:13]=2[CH2:12][C@H:11]([C:20]([CH3:22])=[CH2:21])[CH2:10][CH2:9]1)=[O:16].[OH-].[Na+].[O-]S([O-])(=O)=O.[Mg+2]>C(OCC)C>[CH3:19][C@@H:18]1[C:13]2[CH2:12][C@H:11]([C:20]([CH3:22])=[CH2:21])[CH2:10][CH2:9][C@H:8]([CH3:7])[C:14]=2[C@H:15]([OH:16])[CH2:17]1.[CH3:19][C@@H:18]1[C:13]2[CH2:12][C@H:11]([C:20]([CH3:22])=[CH2:21])[CH2:10][CH2:9][C@H:8]([CH3:7])[C:14]=2[C@@H:15]([OH:16])[CH2:17]1

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 24083Sulfuric acid magnesium salt (1:1)HCID 5321003RotundoneHCID 21226445Aluminium lithium hydride

Product 2

HCID 66615714HCID 66615714, compoundYield 21%HCID 66615728HCID 66615728, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-70 °C

Procedure

At −70° C., a suspension of lithium aluminium hydride (0.52 g, 13.7 mmol) in diethyl ether (30 ml) was treated dropwise within 10 min. with a solution of (−)-rotundone ((3S,5R,8S)-3,4,5,6,7,8-hexahydro-3,8-dimethyl-5-(1-methylethenyl)-1(2H)-azulenone; 3.0 g, 13.7 mmol) in diethyl ether (20 ml). The resulting mixture was stirred for 1 h at −70° C., treated dropwise with a 2M aqueous NaOH solution (2.5 ml) while the reaction temperature rose to −20° C., stirred for 20 min., treated with MgSO4 (5 g), stirred for 10 min., filtered, and the solvent evaporated. Flash chromatography (400 g 0.015-0.040 mm-SiO2, flow: 80 ml/min., hexane/methyl t-butyl ether 100:0 to 85:15 in 30 min.) of the crude product (2.8 g, GC: 65:35 (1R)/(1S)-epimer) gave (1R,3S,5R,8S)-3,8-dimethyl-5-(prop-1-en-2-yl)-1,2,3,4,5,6,7,8-octahydroazulen-1-ol (1.07 g, 35%) and (1S,3S,5R,8S)-3,8-dimethyl-5-(prop-1-en-2-yl)-1,2,3,4,5,6,7,8-octahydroazulen-1-ol (0.64 g, 21%).

Workup

  1. customrose to −20° C.
  2. stirringstirred for 20 min.
  3. stirringstirred for 10 min.
  4. filtrationfiltered
  5. customthe solvent evaporated

Sources & evidence

ORD record
ord-6ff56264118d4865af8415d6fdab81c9
Source dataset
uspto-grants-2014_11
Patent number
US08883468B2

Reaction notes

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