Diethyl Ether → 3-[4-(3-Hydroxy-2,2-dimethoxypropoxymethyl)benzylidene]-4,7,7-trimethylbicyclo[2.2.1]heptan-2-one

HRID 251521Notes

Reaction equation

HRID 251521 reaction equation
Br[CH2:2][C:3]1[CH:20]=[CH:19][C:6]([CH:7]=[C:8]2[C:13]3([CH3:17])[C:14]([CH3:16])([CH3:15])[CH:10]([CH2:11][CH2:12]3)[C:9]2=[O:18])=[CH:5][CH:4]=1.[CH3:21][O:22][C:23]([O:28][CH3:29])([CH2:26][OH:27])[CH2:24][OH:25].CC([O-])(C)C.[K+].C(OCC)C>C1COCC1.CC(O)(C)C.O>[OH:25][CH2:24][C:23]([O:28][CH3:29])([O:22][CH3:21])[CH2:26][O:27][CH2:2][C:3]1[CH:20]=[CH:19][C:6]([CH:7]=[C:8]2[C:13]3([CH3:17])[C:14]([CH3:16])([CH3:15])[CH:10]([CH2:11][CH2:12]3)[C:9]2=[O:18])=[CH:5][CH:4]=1

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 111263102,2-Dimethoxypropane-1,3-diolHCID 23665647Potassium tert-butoxideHCID 67292023HCID 67292023, compound

Product 1

HCID 672911983-[4-(3-Hydroxy-2,2-dimethoxypropoxymethyl)benzylidene]-4,7,7-trimethylbicyclo[2.2.1]heptan-2-one

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

A solution of 3-(4-bromomethylbenzylidene)-4,7,7-trimethylbicyclo[2.2.1]-heptan-2-one (C. Bouillon, C. Vayssie, in Ger. Offen., (Oreal S. A., Fr.). Appl: DE 19780314. 78-2811041, 1978, p. 71. C. Bouillon, C. Vayssie, in Fr. Demande, (Oreal S. A., Fr.), Fr, Number 2421878, 1979, p. 31. C. Bouillon, C. Vayssie, (Oreal S. A., Fr.). Ca, Number 1113480, 1981, p. 61) (10.0 g, 30 mmol) in THF (30 ml) is slowly added dropwise at 40° C. with stirring to a solution of 2,2-dimethoxy-1,3-propanediol (M. W. Chun, D. H. Shin, H. R. Moon, J. Lee, H. Park, L. S. Jeong, Bioorg. Med. Chem. Lett 1997, 7, 1475. E. Cesarotti, P. Antognazza, M. Pallavicini, L. Villa, Helv. Chim. Acta 1993, 76, 2344. E. L. Ferroni, V. DiTella, N. Ghanayem, R. Jeske, C. Jodlowski, et al., J. Org. Chem. 1999, 64, 4943) (8.17 g, 60 mmol) and t-BuOK (4.50 g, 40 mmol) in t-BuOH (150 ml). E is stirred at 40° C. for 30 min and subsequently at the reflux temperature for 1 h. After the reaction mixture has been cooled, diethyl ether (30 ml) and water (100 ml) are added. The organic phase is separated off, and the aqueous phase is extracted with diethyl ether (3×50 ml). The combined organic phases are washed with saturated sodium chloride solution (3×70 ml) and dried over magnesium sulfate; the solvent is removed. Work-up by column chromatography using ethyl acetate:cyclohexane 1:1 gives

Workup

  1. temperatureAfter the reaction mixture has been cooled
  2. customThe organic phase is separated off
  3. extractionthe aqueous phase is extracted with diethyl ether (3×50 ml)
  4. washThe combined organic phases are washed with saturated sodium chloride solution (3×70 ml)
  5. dry with materialdried over magnesium sulfate
  6. customthe solvent is removed
  7. customgives

Sources & evidence

ORD record
ord-123912082d0a4e4ca6f8eb6422a392a2
Source dataset
uspto-grants-2011_01
Patent number
US07863478B2

Reaction notes

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