1-Bromoheptane → HCID 551435, compound

HRID 1946232Notes

Reaction equation

HRID 1946232 reaction equation
[Mg].Br[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9].[CH:10](=[O:14])/[CH:11]=[CH:12]/[CH3:13].[Cl-].[NH4+]>C1(C)C=CC=CC=1.O.BrCCCCCCC.C(O)(=O)C.O1CCCC1>[CH3:13][CH:12]=[CH:11][CH:10]([OH:14])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9]

Participants

10

Reactant 4

HCID 123691-BromoheptaneHCID 25517Ammonium ChlorideHCID 447466CrotonaldehydeHCID 5462224Magnesium

Product 1

HCID 551435HCID 551435, compoundYield 82.1%

Reagents, catalysts & solvents 5

HCID 123691-BromoheptaneCatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
10 °C

Procedure

Under an atmosphere of nitrogen the flask is charged with 121 g magnesium and 720 g tetrahydrofuran. The Grignard-reaction is started with 5 g bromo-heptane. Then, a solution of 908 g bromo-heptane in 1000 g toluene is added dropwise within 260 minutes under stirring. The reaction mixture is kept between 55 and 60° C. The resulting dark solution is cooled to 10° C. and a solution of 357 g crotonaldehyde in 500 g toluene is added dropwise within 105 minutes, during which the pot temperature is kept between 10 and 20° C. with an ice-water bath. The resulting grey-brown suspension is continued to stir for 20 minutes at max. 20° C. and then poured, under vigorous stirring, into a mixture of 2 kg ice and 1 l aqueous saturated ammonium chloride solution. The mixture is diluted with 4 l water and buffered with 300 ml acetic acid. The phases are separated. The organic layer is washed with 4 l and 2 l hot water. The organic phase is concentrated in vacuo to give 864 g crude product as a pale yellow oil. This is distilled at 0.1 mbar over a 10 cm-Raschig ring column. Fractions boiling between 85 and 90° C. were collected to give 709 g undec-2-en-4-ol.

Workup

  1. customis kept between 55 and 60° C
  2. customis kept between 10 and 20° C. with an ice-water bath
  3. stirringto stir for 20 minutes at max
  4. customThe phases are separated
  5. washThe organic layer is washed with 4 l and 2 l hot water
  6. concentrationThe organic phase is concentrated in vacuo
  7. customto give 864 g crude product as a pale yellow oil
  8. distillationThis is distilled at 0.1 mbar over a 10 cm-Raschig ring column
  9. customboiling between 85 and 90° C.
  10. customwere collected

Sources & evidence

ORD record
ord-2a1020dddc6d4c6fa6d7e08e12ee7f55
Source dataset
uspto-grants-2013_03
Patent number
US08399399B2

Reaction notes

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