Hydrochloric Acid → 5-Ethenyl-4,4a,7,8-tetrahydro-3-(hydroxymethylene)-4a-methyl-2(3H)-naphthalenone

HRID 1660142Notes

Reaction equation

HRID 1660142 reaction equation
[CH:1]([C:3]1[C:4]2([CH3:14])[C:9]([CH2:10][CH2:11][CH:12]=1)=[CH:8][C:7](=[O:13])[CH2:6][CH2:5]2)=[CH2:2].C[O-].[Na+].[CH:18](OC)=[O:19].Cl>O1CCCC1>[CH:1]([C:3]1[C:4]2([CH3:14])[C:9]([CH2:10][CH2:11][CH:12]=1)=[CH:8][C:7](=[O:13])[C:6](=[CH:18][OH:19])[CH2:5]2)=[CH2:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7865Methyl formateHCID 10942334Sodium MethoxideHCID 10976251AGN-PC-0NDSYB

Product 1

HCID 705048585-Ethenyl-4,4a,7,8-tetrahydro-3-(hydroxymethylene)-4a-methyl-2(3H)-naphthalenoneYield 96.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-5 °C

Procedure

A solution of 50.0 g (0.265 mol) of 5-ethenyl-4,4a,7,8-tetrahydro-4a-methyl-2(3H)-naphthalenone in 350 mL of tetrahydrofuran was cooled to -5° C. in an ice-methanol bath and stirred under nitrogen while 57.2 g (1.06 mol) of sodium methoxide was added. The resulting mixture was stirred for 30 min at -5° C. and then a solution of 114 mL (1.85 mol) of methyl formate in 100 mL of tetrahydrofuran was added slowly. The mixture was stirred overnight at room temperature and then poured onto a mixture of ice-water (1500 mL) and 6 N hydrochloric acid (265 mL). The product was extracted with ether and the combined extracts were washed with water. The dried extract was dried over anhydrous magnesium sulfate and concentrated in vacuo to afford an oil. This oil was triturated with hexane (4×250 mL) and the combined triturates were dried over magnesium sulfate and concentrated in vacuo to afford 55.37 g of a red oil, consisting essentially of the above-entitled compound as established by proton NMR (PMR) spectral data.

Workup

  1. additionwas added
  2. stirringThe mixture was stirred overnight at room temperature
  3. extractionThe product was extracted with ether
  4. washthe combined extracts were washed with water
  5. extractionThe dried extract
  6. dry with materialwas dried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customto afford an oil
  9. customThis oil was triturated with hexane (4×250 mL)
  10. dry with materialthe combined triturates were dried over magnesium sulfate
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3407f3213ca841ac976c6a77c5a751bb
Source dataset
uspto-grants-1981_12
Patent number
US04307102

Reaction notes

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