Ammonium Chloride → (R)-(+)-tert. Butyl 2,6-dimethyl-4-heptenyl ether

HRID 1701251ノート

反応式

HRID 1701251 の反応式
[I-].[CH2:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH:3]([CH3:5])[CH3:4].C([Li])CCC.[C:30]([O:34][CH2:35][C@H:36]([CH3:40])[CH2:37][CH:38]=O)([CH3:33])([CH3:32])[CH3:31].[NH4+].[Cl-].C([C@H](O[C@@H](C(C)(C)C)C(C)CC=CC(C)C)C(C)CC=CC(C)C)(C)(C)C>CCCCCC.C1C=CC=CC=1.O1CCCC1>[CH3:40][C@H:36]([CH2:37][CH:38]=[CH:2][CH:3]([CH3:5])[CH3:4])[CH2:35][O:34][C:30]([CH3:33])([CH3:32])[CH3:31]

参加物

9

反応物 5

HCID 25517Ammonium ChlorideHCID 12923323(R)-4-tert. butoxy-3-methylbutanalHCID 18386505Isobutyltriphenylphosphonium iodideHCID 131711725(R)-(+)-tert. butyl-2,6-dimethyl-4-heptenyl etherHCID 178418339Butyllithium

生成物 1

HCID 131711724(R)-(+)-tert. Butyl 2,6-dimethyl-4-heptenyl ether

試薬・触媒・溶媒 3

HCID 241Benzene溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒2 回

実験手順

A slurry of 2.67 g. (6 mmoles) of isobutyl triphenylphosphonium iodide in 50 ml. of dry tetrahydrofuran was stirred at 0° C. while a solution of 2.94 ml. (6 mmoles) of 2.04 M n-butyllithium in hexane was added dropwise. The resulting mixture was stirred for 10 minutes and then treated with a solution of 0.475 g. (3 mmoles) of (R)-4-tert. butoxy-3-methylbutanal in 25 ml. of dry tetrahydrofuran. After the addition was complete, the reaction mixture was stirred for one hour at room temperature then treated with saturated aqueous NH4Cl and worked up with hexane in the usual manner. The crude product (0.792 g.) was chromatographed on 25 g. of silica gel. Elution with 9:1 parts by volume hexane-ether followed by evaporative distillation gave 0.418 g. (70.4%) of (R)-(+)-tert. butyl-2,6-dimethyl-4-heptenyl ether as a colorless liquid, b.p. 75°-80° C. (bath temperature) (10 mm Hg.); [α]D25 +11.44° (c 0.61, C6H6).

後処理

  1. additiontreated with a solution of 0.475 g
  2. additionAfter the addition
  3. stirringthe reaction mixture was stirred for one hour at room temperature
  4. customThe crude product (0.792 g.) was chromatographed on 25 g
  5. washElution with 9:1 parts by volume hexane-ether
  6. distillationfollowed by evaporative distillation
  7. customgave 0.418 g

出典と根拠

ORDレコード
ord-8c645dbd372b40998f1d58025fdee00e
出典データセット
uspto-grants-1980_03
特許番号
US04191842

反応ノート

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