Tetrahydrofuran → Methyl [2-(3,5-dimethoxyphenyl)cyclohexylidene]acetate

HRID 483005Notes

Reaction equation

HRID 483005 reaction equation
[H-].[Na+].O1CCC[CH2:4]1.C[C:9](P(OC)(O)=O)([C:11]([O-:13])=[O:12])[CH3:10].[CH3:19][O:20][C:21]1[CH:22]=[C:23]([CH:29]2C[CH2:33][CH2:32][CH2:31][C:30]2=O)[CH:24]=[C:25]([O:27][CH3:28])[CH:26]=1>O.C(O)(=O)C>[CH3:28][O:27][C:25]1[CH:24]=[C:23]([CH:29]2[CH2:30][CH2:31][CH2:32][CH2:33][C:10]2=[CH:9][C:11]([O:13][CH3:4])=[O:12])[CH:22]=[C:21]([O:20][CH3:19])[CH:26]=1

Participants

7

Reactant 4

HCID 8028Tetrahydrofuran3×HCID 24758Sodium hydrideHCID 133666722-(3,5-Dimethoxyphenyl)cyclohexan-1-oneHCID 53413272Trimethylphosphonoacetate

Product 1

HCID 54436910Methyl [2-(3,5-dimethoxyphenyl)cyclohexylidene]acetate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

To a suspension of 3.9 g. (0.081 mole) 50% sodium hydride in 500 ml. anhydrous tetrahydrofuran (THF) was added dropwise at room temperature a solution of 16.2 g. (0.089 mole) trimethylphosphonoacetate in 50 ml. THF and the mixture stirred for 15 minutes. A solution of 17.4 g. (0.074 mole) 2-(3,5-dimethoxyphenyl)cyclohexanone in 100 ml. THF was added in portions after which the mixture was heated at 70° C. for three hours and cooled to 0° C. Glacial acetic acid, 5.4 g., was added and the resulting mixture diluted with water and extracted with ethyl acetate. The extracts were dried (Na2SO4) and evaporated to give 22 g. of crude product which was crystallized from isopropyl ether; 20.4 g., M.P. 80°-81° C. 1H-NMR (CDCl3) ppm (delta): 3.60 (s, 3H, COOCH3), 3.80 (s, 6H, OCH3), 5.20 (s, 1H, olefin), 6.34 (s, 3H, aromatic). Mass spectrum, exact mass for C17H24O4 : 292.3783. Found: 292.1658.

Workup

  1. additionTo a suspension of 3.9 g
  2. temperaturecooled to 0° C
  3. addition, was added
  4. extractionextracted with ethyl acetate
  5. dry with materialThe extracts were dried (Na2SO4)
  6. customevaporated
  7. customto give 22 g
  8. customof crude product which was crystallized from isopropyl ether

Sources & evidence

ORD record
ord-0bf8a647d2154bdd9c51b5ef3ca2eef7
Source dataset
uspto-grants-1986_03
Patent number
US04576964

Reaction notes

Loading…