Adamantanone → [(3-Tert-butyldimethylsilyloxy-4-methoxyphenyl)methoxy methylene]adamantane

HRID 369522ノート

反応式

HRID 369522 の反応式
[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[C:2]1=O)[CH2:8]2.[Si:12]([O:19][C:20]1[CH:21]=[C:22]([CH:27]=[CH:28][C:29]=1[O:30][CH3:31])[C:23]([O:25][CH3:26])=O)([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13].[H-].[Al+3].[Li+].[H-].[H-].[H-]>O1CCCC1.[Cl-].[Cl-].[Cl-].[Ti+3]>[Si:12]([O:19][C:20]1[CH:21]=[C:22]([CH2:23][O:25][CH:26]=[C:2]2[CH:3]3[CH2:9][CH:7]4[CH2:6][CH:5]([CH2:10][CH:1]2[CH2:8]4)[CH2:4]3)[CH:27]=[CH:28][C:29]=1[O:30][CH3:31])([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:13])[CH3:14]

参加物

6

反応物 3

HCID 64151AdamantanoneHCID 11335452Methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoateHCID 21226445Aluminium lithium hydride

生成物 1

HCID 19969138[(3-Tert-butyldimethylsilyloxy-4-methoxyphenyl)methoxy methylene]adamantane収率 20.9%

試薬・触媒・溶媒 2

HCID 10313229titanium(III) trichloride触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

2-Adamantanone (Aldrich, 55 mg, 0.37 mmol) and methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoate (90 mg, 0.30 mmol, prepared as in Step 2, above) were mixed and dissolved in 0.9 ml of anhydrous tetrahydrofuran (THF). Lithium aluminum hydride (51 mg, 1.34 mmol) was added with stirring to an ice-cold mixture of titanium trichloride (Aldrich, 440 mg, 2.85 mmol) in THF under nitrogen. The ice-bath was removed and triethylamine was added to the mixture. After refluxing for 1 hr, the 2-adamantanone--methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoate mixture was introduced via a syringe pump over 5 hr period. The mixture was refluxed and stirred for 4 additional hours. After cooling to room temperature, the black mixture was partitioned three times between saturated sodium bicarbonate solution and ethyl acetate . The combined extracts were washed with water and brine and dried over magnesium sulfate. The solution was evaporated to give a tan solid which was flash-chromatographed over silica gel. Elution with hexane/ethylacetate (15:1) afforded 26 mg of [(3-tert-butyldimethylsilyloxy-4-methoxyphenyl)methoxy methylene]adamantane as a colorless oil. NMR(δ): 0.18 (s, 6H), 1.00 (s, 9H), 3.30 (s, 3H), 3.85 (s, 3H).

後処理

  1. customThe ice-bath was removed
  2. additiontriethylamine was added to the mixture
  3. temperatureAfter refluxing for 1 hr
  4. additionthe 2-adamantanone--methyl 3-tert-butyldimethylsilyloxy-4-methoxybenzoate mixture was introduced via a syringe pump over 5 hr period
  5. temperatureThe mixture was refluxed
  6. customthe black mixture was partitioned three times between saturated sodium bicarbonate solution and ethyl acetate
  7. washThe combined extracts were washed with water and brine
  8. dry with materialdried over magnesium sulfate
  9. customThe solution was evaporated
  10. customto give a tan solid which
  11. customwas flash-chromatographed over silica gel
  12. washElution with hexane/ethylacetate (15:1)

出典と根拠

ORDレコード
ord-d0d8093229ae464ea7a6b8828b4470d7
出典データセット
uspto-grants-2000_10
特許番号
US06139781

反応ノート

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