Adamantanone → Biadamantylidene

HRID 893442

반응식

HRID 893442 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.[Na]>[Cl-].[Cl-].[Cl-].[Ti+3].O1CCOCC1>[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[C:2]1=[C:2]1[CH:3]3[CH2:9][CH:7]4[CH2:6][CH:5]([CH2:10][CH:1]1[CH2:8]4)[CH2:4]3)[CH2:8]2

참가 물질

5

반응물 2

HCID 64151Adamantanone2회HCID 5360545Sodium

생성물 1

HCID 141567Biadamantylidene수율 97%

시약·촉매·용매 2

HCID 10313229titanium(III) trichloride촉매HCID 312751,4-Dioxane용매

실험 절차

One (1) part of adamantanone was treated with 1.5 parts of TiCl3 and 4.5 parts Na. Titanium trichloride (2.314 grams, 15.0 mmol) was weighed into a 3-necked flask in an argon glove bag. The flask was cooled over ice, and 25 ml of dry 1,4-dioxane was added with stirring. Small (about 5 mm) chunks of Na metal were added (1.035 grams, 45.0 mmol). The mixture refluxed with stirring under an argon blanket for 45 minutes. No sodium particles were visible. The adamantanone (1.502 grams, 10.0 mmol) was added to the mixture and reflux was continued for 23 additional hours. After cooling, 50 ml of hexanes was added. The product mixture was filtered through Florisil and the filter cake was washed with additional hexanes. NMR analysis of the recovered product revealed essentially pure dimer, with neither unreacted ketone nor byproduct alcohol detected. The dimer, olefin, adamantylideneadamantane was produced in 97% yield.

후처리

  1. additionwas added
  2. additionSmall (about 5 mm) chunks of Na metal were added (1.035 grams, 45.0 mmol)
  3. temperatureThe mixture refluxed
  4. stirringwith stirring under an argon blanket for 45 minutes
  5. temperaturereflux
  6. temperatureAfter cooling
  7. filtrationThe product mixture was filtered through Florisil
  8. washthe filter cake was washed with additional hexanes

출처 및 근거

ORD 기록
ord-d79e4fd1e9514b79b542ac66889264f7
출처 데이터셋
uspto-grants-1992_06
특허 번호
US05124498

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