Sodium Carbonate → 3a,6-Epoxy-7-isopropyl-1,4-dimethyl-2,3,3a,4,5,6,7,8-octahydroazulene

HRID 597343Notes

Reaction equation

HRID 597343 reaction equation
[CH:1]([CH:3]([CH:14]([CH3:16])[CH3:15])[CH2:4][C:5]1[CH:9]([C:10]([CH3:12])=[CH2:11])[CH2:8][CH2:7][C:6]=1[CH3:13])=[O:2].[Sn](Cl)(Cl)(Cl)Cl.C(=O)([O-])[O-].[Na+].[Na+]>[N+](C)([O-])=O>[O:2]1[CH:1]2[CH2:11][CH:10]([CH3:12])[C:9]31[C:5]([CH2:4][CH:3]2[CH:14]([CH3:16])[CH3:15])=[C:6]([CH3:13])[CH2:7][CH2:8]3

Participants

5

Reactant 3

HCID 10340Sodium CarbonateHCID 24287Tin tetrachlorideHCID 213885282-(2-Formyl-3-methylbutyl)-3-isopropenyl-1-methyl-1-cyclopentene

Product 1

HCID 214349033a,6-Epoxy-7-isopropyl-1,4-dimethyl-2,3,3a,4,5,6,7,8-octahydroazuleneYield 78.8%

Reagents, catalysts & solvents 1

HCID 6375NitromethaneSolvent2×

Procedure

To a solution, cooled to -40°, of 3.3 g of 2-(2-formyl-3-methylbutyl)-3-isopropenyl-1-methyl-1-cyclopentene in 225 ml of nitromethane were added 45 ml of a 0.5-M solution of tin tetrachloride in nitromethane. The reaction mixture became intensely yellow in colour and an initially resulting precipitate dissolved again. The mixture was treated immediately with excess 2-N sodium carbonate solution and extracted with ether. After washing, the ethereal phase was dried in a conventional manner and the solvent was removed. Distillation under a high vacuum yielded 2.6 g of crude 3a,6-epoxy-7-isopropyl-1,4-dimethyl-2,3,3a,4,5,6,7,8-octahydroazulene in the form of a colourless oil which could be separated by chromatography on 40 times the amount of Florisil (magnesium silicte gel) with hexane/ether (19:1) into two pairs of epimers (A and B). Epimer A: b.p.0.01 ca 75°; IR(film): νmax = 1465/40, 1380, 1345, 1245, 1162, 1125, 1108, 1080, 1050, 995, 965, 945, 910, 880 cm- 1. The odour is camphorous, woody. Epimer B: b.p.0.01 ca 80° IR(film): νmax = 1465/35, 1380, 1340, 1295, 1245, 1200/1195, 1170, 1145, 1110, 1060, 1030, 1000, 990, 950, 925, 910, 878 cm- 1. The odour is camphorous, dull.

Workup

  1. customan initially resulting precipitate
  2. dissolutiondissolved again
  3. extractionextracted with ether
  4. washAfter washing
  5. customthe ethereal phase was dried in a conventional manner
  6. customthe solvent was removed
  7. distillationDistillation under a high vacuum

Sources & evidence

ORD record
ord-62779b57d18846b1a8d01f3b2008a71b
Source dataset
uspto-grants-1977_03
Patent number
US04013726

Reaction notes

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