Chlorodimethylaluminum → (R)-1-Chloro-6-trimethylsilanyl-hex-4-yn-2-ol

HRID 581616ノート

反応式

HRID 581616 の反応式
[CH2:1]([Si:4]([CH3:7])([CH3:6])[CH3:5])[C:2]#[CH:3].[Li]CCCC.[Al](Cl)(C)C.[CH2:17]([C@@H:19]1[O:21][CH2:20]1)[Cl:18]>C1(C)C=CC=CC=1>[Cl:18][CH2:17][C@H:19]([OH:21])[CH2:20][C:3]#[C:2][CH2:1][Si:4]([CH3:7])([CH3:6])[CH3:5]

参加物

6

反応物 4

HCID 79147ChlorodimethylaluminumHCID 83378Trimethyl-2-propynylsilaneHCID 2734062(-)-EpichlorohydrinHCID 178418339Butyllithium

生成物 1

HCID 21310064(R)-1-Chloro-6-trimethylsilanyl-hex-4-yn-2-ol収率 66.6%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

実験手順

14.11 g (126 mmol) of propargyltrimethylsilane was dissolved in 125 ml of abs. toluene and cooled to -17°. 81.1 ml of nBuLi (1.55M, hexane) was slowly added while keeping the temperature below -5°. 5 Minutes later, 126 ml of Me2AlCl (1M, hexane) was added to this solution of the Li-acetylide. The temperature was then lowered to -45° and 6.90 ml of (R)-epichlorohydrine (88 mmol), dissolved in 50 ml of toluene, was added. The cooling bath was then removed and the reaction mixture allowed to reach ambient temperature during 24 h. After careful quenching with icecold water and filtration, the product was extracted with ether, washed with NH4Cl, dried over sodium sulfate and the solvents removed i. V. Flash chromatography (SiO2, hexane/AcOEt=86/14) yielded 12.01 g of (R)-1-chloro-6-trimethylsilanyl-hex-4-yn-2-ol as colorless oil, 97% pure according to GC.

後処理

  1. customthe temperature below -5°
  2. customwas then lowered to -45°
  3. additionwas added
  4. customThe cooling bath was then removed
  5. customAfter careful quenching with icecold water and filtration
  6. extractionthe product was extracted with ether
  7. washwashed with NH4Cl
  8. dry with materialdried over sodium sulfate
  9. customthe solvents removed i

出典と根拠

ORDレコード
ord-8c2604e7c6b74d7d8b0146df22061afa
出典データセット
uspto-grants-1999_07
特許番号
US05919986

反応ノート

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