Adamantanone → Biadamantylidene

HRID 893442

反応式

HRID 893442 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.[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

参加物

5

反応物 2

HCID 64151Adamantanone2 回HCID 5360545Sodium

生成物 1

HCID 141567Biadamantylidene収率 97%

試薬・触媒・溶媒 2

HCID 10313229titanium(III) trichloride触媒HCID 312751,4-Dioxane溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-d79e4fd1e9514b79b542ac66889264f7
出典データセット
uspto-grants-1992_06
特許番号
US05124498

関連ノート

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