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

HRID 1701251Notes

Reaction equation

HRID 1701251 reaction equation
[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]

Participants

9

Reactant 5

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent2×

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-8c645dbd372b40998f1d58025fdee00e
Source dataset
uspto-grants-1980_03
Patent number
US04191842

Reaction notes

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