Water → (E)-3,8-diacetoxy-3,7-dimethyl-1,6-octadiene

HRID 1980604Notes

Reaction equation

HRID 1980604 reaction equation
[C:1]([O:4][C:5]([CH3:15])([CH2:8][CH2:9][CH:10](Cl)[C:11]([CH3:13])=[CH2:12])[CH:6]=[CH2:7])(=[O:3])[CH3:2].[C:16]([O-:19])(=[O:18])[CH3:17].[K+].O>CN(C)C(=O)C.O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[C:1]([O:4][C:5]([CH3:15])([CH2:8][CH2:9]/[CH:10]=[C:11](\[CH3:13])/[CH2:12][O:19][C:16](=[O:18])[CH3:17])[CH:6]=[CH2:7])(=[O:3])[CH3:2].[C:1]([O:4][C:5]([CH3:15])([CH2:8][CH2:9]/[CH:10]=[C:11](/[CH3:13])\[CH2:12][O:19][C:16](=[O:18])[CH3:17])[CH:6]=[CH2:7])(=[O:3])[CH3:2].[C:1]([O:4][C:5]([CH3:15])([CH2:8][CH2:9][CH:10]([O:19][C:16](=[O:18])[CH3:17])[C:11]([CH3:13])=[CH2:12])[CH:6]=[CH2:7])(=[O:3])[CH3:2]

Participants

8

Reactant 3

HCID 962WaterHCID 517044Potassium AcetateHCID 111605936-Chloro-7-methylene-3-methyl-1-octen-3-yl acetate

Product 3

HCID 20402282HCID 20402282, compoundYield 5%HCID 204022953,6-Diacetoxy-3,7-dimethyl-1,7-octadieneYield 34%HCID 86740022(E)-3,8-diacetoxy-3,7-dimethyl-1,6-octadieneYield 55%

Reagents, catalysts & solvents 2

HCID 165397Cupric acetate monohydrateCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 3-acetoxy-6-chloro-3,7-dimethyl-1,7-octadiene (11.5 g, 0.05 mol), prepared according to Example 1, potassium acetate (14.7 g, 0.15 mol), and copper (II) acetate monohydrate (2 g, 0.01 mol) in N,N-dimethylacetamide (50 mL) was stirred for 9 h at 100° C. The reaction mixture was poured into water and extracted with diethyl ether. The extracts were washed with 5% sodium bicarbonate (50 mL) and brine (50 mL). Evaporation of the solvent and distillation afforded 9.5 g of distillate as a mixture (GLC) of (E)-3,8-diacetoxy-3,7-dimethyl-1,6-octadiene (55%), (Z)-3,8-diacetoxy-3,7-dimethyl-1,6-octadiene (5%) and 3,6-diacetoxy-3,7-dimethyl-1,7-octadiene (34%). These isomers can be separated by preparative GLC. The (Z)- and (E)-mixture can be separated from the internal diacetoxy derivative by careful distillation. (Z)-isomer: IR (film) 1740, 1370, 1240, 1020 cm-1. NMR (CDCl3) δ 1.53 (3H, s), 1.77 (3H, s), 1.97 (3H, s), 2.03 (3H, s), 1.8-2.4 (4H, complex), 4.57 (2H, s), 5.0-5.67 (3H, m), 6.0 (1H, dd). MS (m/e) 43, 119, 41, 45. (E)-isomer: IR (film) 1740, 1370, 1240, 1020 cm-1. NMR (CDCl3) δ 1.53 (3H, s), 1.64 (3H, s), 1.97 (3H, s), 2.03 (3H, s), 1.8-2.4 (4H, complex), 4.43 (2H, s), 5.0-5.6 (3H, m), 6.0 (1H, dd). MS (m/e) 43, 119, 41, 45. Internal isomer: IR (film) 1740, 1370, 1240, 1020 cm-1. NMR (CDCl3) δ 1.64 (3H, s), 2.00 (3H, s), 2.03 (3H, s), 2.07 (3H, s), 1.8-2.4 (4H, m), 4.33 (1H, m), 4.83-5.50 (4H, m), 6.00 (1H, dd). MS (m/e) 43, 41, 119, 67.

Workup

  1. customprepared
  2. extractionextracted with diethyl ether
  3. washThe extracts were washed with 5% sodium bicarbonate (50 mL) and brine (50 mL)
  4. customEvaporation of the solvent and distillation

Sources & evidence

ORD record
ord-fc168937e7d74eaab98a32d0d2dd47e5
Source dataset
uspto-grants-1985_04
Patent number
US04510319

Reaction notes

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