Hydrochloric Acid → HCID 68725231, compound

HRID 1471398Notes

Reaction equation

HRID 1471398 reaction equation
[CH3:1][C:2]12[O:12][CH:11]1[CH2:10][CH2:9][C:4]1([CH2:8][CH2:7][CH2:6][CH2:5]1)[CH:3]2[C:13]([O:15][CH3:16])=[O:14].[Na].Cl>CO>[OH:12][CH:11]1[CH2:10][CH2:9][C:4]2([CH2:8][CH2:7][CH2:6][CH2:5]2)[C:3]([C:13]([O:15][CH3:16])=[O:14])=[C:2]1[CH3:1]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 5360545SodiumHCID 86647585HCID 86647585, compound

Product 1

HCID 68725231HCID 68725231, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

The crude methyl 1-methyl-7-oxaspiro[bicyclo[4.1.0]heptane-3,1′-cyclopentane]-2-carboxylate obtained (13 g) was added to a solution of sodium (1.5 g, 64 mmol) in methanol (100 ml) and the resulting mixture was refluxed for 10 h, poured into cold 2N aqueous HCl (100 ml), and extracted twice with MTBE (100 ml). The combined organic phases were washed with water (100 ml), twice with a saturated aqueous solution of NaCl (100 ml), dried (MgSO4), concentrated, and gave crude gave methyl 8-hydroxy-7-methylspiro[4.5]dec-6-ene-6-carboxylate (5.65 g) which was dissolved in dichloromethane (80 ml) and treated at −30° C. with triethylsilane (14.4 ml, 0.1 mol) and with BF3.OEt2 (4.7 ml, 37.8 mmol). The resulting mixture was stirred for 3 h while allowing the temperature to reach 20° C., poured into cold 2N aqueous NaOH (80 ml), and extracted twice with MTBE (100 ml). The combined organic phases were washed with water (100 ml), with a saturated aqueous solution of NaCl (100 ml), dried (MgSO4), and concentrated. FC (90 g SiO2, hexane/MTBE 95:5) of the crude product (2.05 g) gave methyl 7-methylspiro[4.5]dec-6-ene-6-carboxylate (1.16 g, 42% three-step overall yield). Boiling point: 105° C. (0.08 mbar).

Workup

  1. temperaturethe resulting mixture was refluxed for 10 h
  2. extractionextracted twice with MTBE (100 ml)
  3. washThe combined organic phases were washed with water (100 ml), twice with a saturated aqueous solution of NaCl (100 ml)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customgave crude

Sources & evidence

ORD record
ord-d55252bf3aed4edd878a75a40beaa741
Source dataset
uspto-grants-2015_04
Patent number
US09012391B2

Reaction notes

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