Carbon Dioxide → 6-Chloro-7-methylene-3-methyl-1-octen-3-yl acetate

HRID 1980603Notes

Reaction equation

HRID 1980603 reaction equation
[C:1]([O:4][C:5]([CH2:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13])([CH:7]=[CH2:8])[CH3:6])(=[O:3])[CH3:2].[Cl:15][O-].[Ca+2].Cl[O-].O.C(=O)=O>ClCCl>[C:1]([O:4][C:5]([CH3:6])([CH2:9][CH2:10][CH:11]([Cl:15])[C:12]([CH3:14])=[CH2:13])[CH:7]=[CH2:8])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 962WaterHCID 8294Linalyl AcetateHCID 24504Calcium hypochlorite

Product 1

HCID 111605936-Chloro-7-methylene-3-methyl-1-octen-3-yl acetateYield 177.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
10 °C

Procedure

A stirred mixture of linalyl acetate (39 g, 0.2 mol), 65% calcium hypochlorite (22 g, 0.1 mol), water (70 mL) and dichloromethane (700 mL) was cooled to 10° C. and solid carbon dioxide was added until an exotherm was no longer observed upon addition. After stirring for an additional 1 h at 10° C., the organic layer was separated and washed successively with a solution containing 5% sodium bicarbonate and 1% sodium bisulfite (100 mL), and then with brine (100 mL). The organic layer was dried, the solvent evaporated, and the residue distilled to yield 41 g of 3-acetoxy-6-chloro-3,7-dimethyl-1,7-octadiene, bp 75°-80° C. (0.5 mm). IR (film) 1740, 1370, 1250, 920 cm-1. NMR (CDCl3) δ1.53 (3H, s), 1.8 (3H, bs), 1.8-2.4 (2H, m), 4.33 (1H, m), 4.84-5.33 (4H, complex) 6.0 (1H, dd).

Workup

  1. additionwas no longer observed upon addition
  2. customthe organic layer was separated
  3. washwashed successively with a solution
  4. additioncontaining 5% sodium bicarbonate and 1% sodium bisulfite (100 mL)
  5. customThe organic layer was dried
  6. customthe solvent evaporated
  7. distillationthe residue distilled

Sources & evidence

ORD record
ord-876afbfc82ee492490bd062be24fc2a3
Source dataset
uspto-grants-1985_04
Patent number
US04510319

Reaction notes

Loading…