Hexane → 3-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetane

HRID 644117Notes

Reaction equation

HRID 644117 reaction equation
[OH-].[Na+].CCCCCC.[CH2:9]([C:11]1([CH2:15][OH:16])[CH2:14][O:13][CH2:12]1)[CH3:10].[Br:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23]Br>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[Br:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][O:16][CH2:15][C:11]1([CH2:9][CH3:10])[CH2:14][O:13][CH2:12]1

Participants

7

Reactant 4

HCID 8058HexaneHCID 123681,6-DibromohexaneHCID 14798Sodium HydroxideHCID 76444Oxt-101

Product 1

HCID 592073103-{[(6-Bromohexyl)oxy]methyl}-3-ethyloxetaneYield 55.4%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolvent

Procedure

To a solution consisting of sodium hydroxide (50% in water, 50 g), hexane (50 ml) and tetrabutylammonium bromide (0.7 g) was added 3-ethyl-3-oxetanemethanol (5.0 g, 43.0 mmol) and 1,6-dibromohexane (30 g, 122.9 mmol). This mixture was heated at reflux for 5 h. After cooling to room temperature, the resulting mixture was diluted with water (100 ml) and extracted with ethyl acetate (3×100 ml). The extracts were combined and dried over sodium sulphate. The solvent was removed under reduced pressure and the residue was purified by column chromatography, eluting with petrol/ethyl acetate (9:1), to give a colourless oil (6.65 g, 55%). 1H NMR (300 MHz, CDCl3): δ (ppm) 4.44 (d, J=5.8 Hz, 2H, OCH2), 4.37 (d, J=5.8 Hz, 2H, OCH2), 3.52 (s, 2H, OCH2), 3.46 (t, J=6.4 Hz, 2H, OCH2), 3.40 (t, J=6.8 Hz 2H, BrCH2), 1.35-1.91 (m, 10H, CH2), 0.88 (t, J=7.5 Hz, 6H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 78.5 (OCH2), 73.4 (OCH2), 71.3 (OCH2), 43.4 (quat.), 33.8 (CH2), 32.7 (CH2), 29.3 (CH2), 27.9 (CH2) 26.8 (CH2), 25.4 (CH2), 8.2 (CH3). MS (m/e): 279 (MH+, 0.1%) □281 (MH+, 0.1%), 248 (3), 250 (3), 83 (89), 55 (100), 41 (86).

Workup

  1. temperatureThis mixture was heated
  2. temperatureat reflux for 5 h
  3. extractionextracted with ethyl acetate (3×100 ml)
  4. dry with materialdried over sodium sulphate
  5. customThe solvent was removed under reduced pressure
  6. customthe residue was purified by column chromatography
  7. washeluting with petrol/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-0b0580fb2f3b458ba56e9f8272bebfb0
Source dataset
uspto-grants-2010_04
Patent number
US07700643B2

Reaction notes

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