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

HRID 974719노트

반응식

HRID 974719 반응식
[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]

참가 물질

6

반응물 3

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

생성물 1

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

시약·촉매·용매 2

HCID 10313229titanium(III) trichloride촉매HCID 8028Tetrahydrofuran용매2회

실험 절차

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-methyl3-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).

후처리

  1. customThe ice-bath was removed
  2. additiontriethylamine was added to the mixture
  3. temperatureAfter refluxing for 1 hr
  4. additionthe 2-adamantanone-methyl3-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)

출처 및 근거

ORD 기록
ord-3c9fab6f606e427097c099729ffb26d4
출처 데이터셋
uspto-grants-1997_03
특허 번호
US05607625

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