Iodine → 6-Hydroxy-6-isopropenyl-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene

HRID 597342Notes

Reaction equation

HRID 597342 reaction equation
[Mg].II.Br[C:5]([CH3:7])=[CH2:6].[CH3:8][C:9]1[CH2:10][CH2:11][CH:12]2[C:18]=1[CH2:17][CH2:16][C:15](=[O:19])[CH2:14][C:13]2=[CH2:20]>O1CCCC1>[OH:19][C:15]1([C:5]([CH3:7])=[CH2:6])[CH2:16][CH2:17][C:18]2[CH:12]([CH2:11][CH2:10][C:9]=2[CH3:8])[C:13](=[CH2:20])[CH2:14]1

Participants

6

Reactant 4

HCID 807IodineHCID 112022-BromopropeneHCID 5462224MagnesiumHCID 214348873-Methyl-8-methylidene-2,4,5,7,8,8a-hexahydroazulen-6(1H)-one

Product 1

HCID 214348966-Hydroxy-6-isopropenyl-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazuleneYield 76%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a Grignard solution, prepared from 1 g of magnesium chips activated with 1 g of iodine, 5 ml of 2-bromopropene and about 100 ml of tetrahydrofuran, were added over 10 minutes 1.76 g of 1-methyl-4-methylen-6-oxo-2,3,3a,4,5,6,7,8-octahydroazulene. The mixture was stirred vigorously for 30 minutes, cooled to 0° and treated with excess ice-cold ammonium chloride solution. The mixture was then extracted with ether, the organic extract washed with carbonate solution and water, dried over magnesium sulphate and concentrated under reduced pressure. The crude product (2.6 g), which was obtained in the form of a yellow oil, was distilled under high vacuum and yielded 1.6 g (yield 76%) of pure 6-hydroxy-6-isopropenyl-1methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene; b.p.0.1 ca 100° IR(film): νmax = 3550, 3090, 1640, 1450/40, 1378, 1330, 1220, 1165, 1105, 1065, 1038, 900/895, 780 cm-1. The compound has a woody, slightly camphorous, somewhat spicy odour.

Workup

  1. temperaturecooled to 0°
  2. additiontreated with excess ice-cold ammonium chloride solution
  3. extractionThe mixture was then extracted with ether
  4. extractionthe organic extract
  5. washwashed with carbonate solution and water
  6. dry with materialdried over magnesium sulphate
  7. concentrationconcentrated under reduced pressure
  8. customThe crude product (2.6 g), which was obtained in the form of a yellow oil
  9. distillationwas distilled under high vacuum

Sources & evidence

ORD record
ord-fd1ecf18074a422c8f423d1b445fc3d3
Source dataset
uspto-grants-1977_03
Patent number
US04013726

Reaction notes

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