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Lithium hexamethyldisilazane → 2-(1-Methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy-2,4,8,12-cyclotetradecatetraene-1-carbonitrile

HRID 486867
ノート
印刷プレビュー

反応式

HRID 486867 の反応式
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].Cl[CH2:12][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=[C:24]([CH:33]([CH3:35])[CH3:34])[CH:25]([O:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[C:26]#[N:27]>O1CCCC1>[CH3:34][CH:33]([C:24]1[C:25]([O:28][Si:29]([CH3:32])([CH3:31])[CH3:30])([C:26]#[N:27])[CH2:12][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=1)[CH3:35].[CH3:35][CH:33]([C:24]1[C:25](=[O:28])[CH2:26][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=1)[CH3:34]
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 2

HCID 2733832Lithium hexamethyldisilazaneHCID 53993800HCID 53993800、化合物

生成物 2

HCID 544770112-(1-Methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy-2,4,8,12-cyclotetradecatetraene-1-carbonitrile収率 83%HCID 570081642-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one収率 16%

試薬・触媒・溶媒 1

HCID 8028
Tetrahydrofuran
溶媒
2 回

実験手順

A solution of lithium bis(trimethylsilyl) amide (5.0 mmol, 0.25 M) in dry tetrahydrofuran (20 ml) is stirred under argon atmosphere on an oil bath at 40° C. and thereto is dropwise added a solution of the cyanohydrin trimethylsilyl ether which is 15-chloro-3-(1-methylethyl)-6,10,14-tri-methyl-2-trimethylsiloxy-3,5,9,13-pentadecatetraenenitrile (378 mg, 0.895 mmol) prepared in Reference Example 5 in dry tetrahydrofuran (15 ml) over 50 minutes. After stirring the mixture at this temperature for 20 minutes, the reaction is quenched by adding a saturated aqueous ammonium chloride solution while stirring on an ice-water bath. After removing tetrahydrofuran by distillation under reduced pressure, the organic layer is extracted with ether. The obtained extract is purified by silica gel column chromatography (n-hexane/ethyl acetate =60:1) to give 2-(1-methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy -2,4,8,12-cyclotetradecatetraene-1-carbonitrile (288 mg, 83%) and 2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraene-1-on (42.9 mg, 16%).

後処理

  1. customthe reaction is quenched
  2. additionby adding a saturated aqueous ammonium chloride solution
  3. stirringwhile stirring on an ice-water bath
  4. customAfter removing tetrahydrofuran
  5. distillationby distillation under reduced pressure
  6. extractionthe organic layer is extracted with ether
  7. extractionThe obtained extract
  8. customis purified by silica gel column chromatography (n-hexane/ethyl acetate =60:1)

出典と根拠

ORDレコード
ord-af998b4612974d1bae1ef6a7f32bcb01
出典データセット
uspto-grants-1994_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05292911

反応ノート

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