Acetic Anhydride → 6-Formyloxy-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene

HRID 597346Notes

Reaction equation

HRID 597346 reaction equation
[OH:1][CH:2]1[CH2:11][CH2:10][C:9]2[CH:5]([CH2:6][CH2:7][C:8]=2[CH3:12])[C:4](=[CH2:13])[CH2:3]1.[C:14](OC(=O)C)(=[O:16])C.C(=O)([O-])[O-].[Na+].[Na+]>N1C=CC=CC=1.C(O)=O>[CH:14]([O:1][CH:2]1[CH2:11][CH2:10][C:9]2[CH:5]([CH2:6][CH2:7][C:8]=2[CH3:12])[C:4](=[CH2:13])[CH2:3]1)=[O:16]

Participants

6

Reactant 3

HCID 7918Acetic AnhydrideHCID 10340Sodium CarbonateHCID 214348863-Methyl-8-methylidene-1,2,4,5,6,7,8,8a-octahydroazulen-6-ol

Product 1

HCID 214349086-Formyloxy-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazuleneYield 87.4%

Reagents, catalysts & solvents 2

HCID 1049PyridineCatalystHCID 284Formic AcidSolvent

Procedure

2.67 g of 6-hydroxy-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene were treated at 0° firstly with half of a mixture of 4.08 g of acetic anhydride, 1.84 g of formic acid and 37 mg of pyridine. The mixture was stirred for 24 hours at room temperature and with exclusion of light. Then the other half of the reagent was added and the mixture stirred for further 24 hours. The solution was poured on to a mixture of ice and sodium carbonate and worked up in a conventional manner. The crude product so obtained (3.18 g) was distilled under high vacuum and yielded 2.70 g (87%) of pure 6-formyloxy-1-methyl-4-methylen-2,3,3a,4,5,6,7,8-octahydroazulene; b.p.0.005 50°; IR(film):νmax = 3120, 1728, 1645, 1460/45, 1190/82, 1015/1000, 905/900 cm- 1. The compound smells woody, cedar-like, slightly ionone-like.

Workup

  1. additionThen the other half of the reagent was added
  2. stirringthe mixture stirred for further 24 hours
  3. customThe crude product so obtained (3.18 g)
  4. distillationwas distilled under high vacuum

Sources & evidence

ORD record
ord-e8fff6345be54349950ab4ed42802b26
Source dataset
uspto-grants-1977_03
Patent number
US04013726

Reaction notes

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