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

HRID 251521ノート

反応式

HRID 251521 の反応式
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

参加物

8

反応物 4

HCID 3283Diethyl EtherHCID 111263102,2-Dimethoxypropane-1,3-diolHCID 23665647Potassium tert-butoxideHCID 672920233-(4-Bromomethylbenzylidene)-4,7,7-trimethylbicyclo[2.2.1]-heptan-2-one

生成物 1

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

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6386tert-Butanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
40 °C

実験手順

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

後処理

  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

出典と根拠

ORDレコード
ord-123912082d0a4e4ca6f8eb6422a392a2
出典データセット
uspto-grants-2011_01
特許番号
US07863478B2

反応ノート

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