tert-Butanol → Cyclohexadiene, 1-methoxy-

HRID 1488792Notes

Reaction equation

HRID 1488792 reaction equation
[C:1]1([O:7][CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li].C(O)(C)(C)C>C(N)CC.C(N)CN.O>[CH3:8][O:7][C:1]1[CH2:6][CH:5]=[CH:4][CH2:3][CH:2]=1.[CH3:8][O:7][C:1]1[CH2:6][CH2:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 3

HCID 6386tert-ButanolHCID 7519Anisole2×HCID 3028194Lithium2×

Product 2

HCID 75098Cyclohexadiene, 1-methoxy-HCID 761561-Methoxycyclohexa-1,4-diene

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3301EthylenediamineSolventHCID 7852PropylamineSolvent

Procedure

Reduction of anisole. Lithium, in small pieces, (8.75 g, 1.25 gram-atoms) was added to a solution of anisole (54 g, 0.5 mol) in n-propylamine (400 mL), ethylenediamine (105 g (1.75 mol) and t-butanol (111 g, 1.5 mol) cooled to -18°. The temperature increased to 12° and then decreased to -5°. After 2 hr all of the lithium had reacted and the reaction mixture was diluted with 800 mL of water added slowly. The mixture was extracted with ether (3×250 mL). The ether extracts were washed with water (3×200 mL) and brine (1×100 mL) and evaporated. The residue was distilled to give 27.5 g (50% of 1-methoxy-1,4-cyclohexadiene containing 10% of 1-methoxy-1,3-cyclohexadiene by glpc and nmr.

Workup

  1. temperaturecooled to -18°
  2. temperatureThe temperature increased to 12°
  3. customdecreased to -5°
  4. additionadded slowly
  5. extractionThe mixture was extracted with ether (3×250 mL)
  6. washThe ether extracts were washed with water (3×200 mL) and brine (1×100 mL)
  7. customevaporated
  8. distillationThe residue was distilled

Sources & evidence

ORD record
ord-cc8bc8cfead04769a3ba98b48c9fe31b
Source dataset
uspto-grants-1997_10
Patent number
US05675038

Reaction notes

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