Water → HCID 535115, compound

HRID 1904068Notes

Reaction equation

HRID 1904068 reaction equation
O.[CH2:2](I)I.[CH3:5][C:6]1[CH2:11][CH2:10][CH2:9][C:8]([CH3:13])([CH3:12])[C:7]=1[CH2:14][OH:15]>CC(O)=O.[Zn]>[CH3:13][C:8]1([CH3:12])[CH2:9][CH2:10][CH2:11][C:6]2([CH3:2])[C:7]1([CH2:14][OH:15])[CH2:5]2

Participants

6

Reactant 3

HCID 962WaterHCID 6346DiiodomethaneHCID 1116642,6,6-Trimethylcyclohexene-1-methanol

Product 1

HCID 535115HCID 535115, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
-5 °C

Procedure

A solution of 0.4 g of Cu(OAc2).H2O in 20 mL of hot HOAc was treated with 8.8 g (0.13 g-atom) of Zn dust with shaking for 3 min, and the acid was decanted. The Zn-Cu couple was washed by decantation with 30 mL of 1:1 HOAc/Et2O, followed by Et2O (6×30 mL). Next, 20 mL of Et2O was added together with a crystal of I2. A mixture of 18.8 g (70 mmol) of CH2I2 and 3.08 g (20 mmol) of β-cyclogeraniol (l) was added dropwise over a 20-min period, with warming to maintain a gentle reflux. Heating at reflux was continued for an additional 2 h. The cooled solution was decanted, the residue was washed with Et2O, and the total Et2O volume was brought to 200 mL. The solution was cooled in ice/H2O, and pyridine (8 to 9 mL) was added dropwise until no further ZnI2 -pyridine complex separated. The reaction was cooled to -5° C. overnight, filtered twice, and evaporated. Further complex separated on evaporation. TLC (9:1 hexane/EtOAc) demonstrated a single product. The crude oil was eluted through a 3×25 cm silica gel column by 9:1 hexane/Et2O, followed by 1:1 hexane/Et2O. The spectrally pure, colorless oil weighed 3.4 g (quant): IR (film) 3400 (OH), 1460, 1385, 1365, 1155, 1035, 1010, 705 cm-1 ; 1H NMR (CDCl3) δ0.22 (d, J=4.5 Hz, 1, cyclopropyl H), 0.49 (d, J=4.5 Hz, 1, cyclopropyl H), 0.99 (s, 3, CH3), 1.21 (s, 3, CH3), 1.26 (s, 3, CH3), 1.0-1.8 [m, 7, (CH2)3, OH], 3.51 and 3.92 (d, J=12 Hz, 1, and dd, J=12 and 3.5 Hz, 1, CH2O); 13C NMR (CDCl3), 65.8, 38.0, 35.5, 31.9, 31.3, 29.2, 27.4, 23.9, 22.5, 21.7, 18.0 ppm; MS calcd for C11H20O 168.1514, found 168.1521.

Workup

  1. customthe acid was decanted
  2. washThe Zn-Cu couple was washed by decantation with 30 mL of 1:1 HOAc/Et2O
  3. additionNext, 20 mL of Et2O was added together with a crystal of I2
  4. additionwas added dropwise over a 20-min period
  5. temperaturewith warming
  6. temperatureto maintain a gentle reflux
  7. temperatureHeating
  8. temperatureat reflux
  9. waitwas continued for an additional 2 h
  10. customThe cooled solution was decanted
  11. washthe residue was washed with Et2O
  12. temperatureThe solution was cooled in ice/H2O
  13. additionpyridine (8 to 9 mL) was added dropwise until no further ZnI2 -pyridine complex
  14. customseparated
  15. filtrationfiltered twice
  16. customevaporated
  17. customFurther complex separated on evaporation
  18. washThe crude oil was eluted through a 3×25 cm silica gel column by 9:1 hexane/Et2O

Sources & evidence

ORD record
ord-b0dd0680fc8d4202ac720165f1db7546
Source dataset
uspto-grants-1984_03
Patent number
US04439614

Reaction notes

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