Benzyl Bromide → Diethyl 11-(benzyloxy)undecylphosphonate

HRID 85002Notes

Reaction equation

HRID 85002 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][P:13](=[O:20])([O:17][CH2:18][CH3:19])[O:14][CH2:15][CH3:16].C1OCCOCCOCCOCCOCCOC1.[H-].[Na+].[CH2:41](Br)[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1>C(OCC)(=O)C.ClCCl.O1CCCC1>[CH2:41]([O:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][P:13](=[O:20])([O:14][CH2:15][CH3:16])[O:17][CH2:18][CH3:19])[C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1

Participants

8

Reactant 4

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 2855718-Crown-6HCID 45158972Diethyl (11-hydroxyundecyl)phosphonate

Product 1

HCID 86664727Diethyl 11-(benzyloxy)undecylphosphonateYield 42%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Diethyl 11-hydroxyundecylphosphonate (4.0 g, 13.0 mmol) and 18-crown-6 (spatula tip) were added to anhydrous tetrahydrofuran under inert atmosphere. Sodium hydride (312 mg, 13.0 mmol) was added and the solution allowed to stir for 10 minutes. Benzyl bromide (2.4 mL, 19.5 mmol) was then added and the reaction stirred at reflux for 4 hours. After cooling to room temperature, dichloromethane was added and the mixture washed with water and brine. The organic layer was collected, dried over magnesium sulfate, and concentrated under reduced pressure to yield a liquid. Column chromatography (stationary phase:silica, mobile phase:ethyl acetate) was used to isolate the desired product (Rf=0.70, ethyl acetate) as a clear oil (2.173 g, 42% yield). 1H NMR (500.13 MHz, CD2Cl2) δ 7.36-7.29 (m, 4H), 7.29-7.23 (m), 4.47 (2H), 4.10-3.97 (m, 4H), 3.45 (t, J=6.62 Hz, 2H), 1.72-1.62 (m, 2H), 1.62-1.48 (m, 4H), 1.40-1.20 (m, 20H). 13C{1H} NMR (100.62 MHz, CD2Cl2) δ 139.4, 128.6 (2C), 127.9 (2C), 127.7, 73.03, 70.88, 61.57 (d, J=6.4 Hz, 2C), 30.95 (d, J=16.8 Hz), 30.17, 29.94, 29.91, 29.85, 29.75, 29.48, 26.58, 25.91 (d, J=139.8 Hz), 22.78 (d, J=5.3 Hz), 16.68 (d, J=5.9 Hz, 2C). 31P{1H} NMR (202.45 MHz, CD2Cl2): δ 32.83. Analysis calculated (found) %: C 66.30 (65.66), H 9.86 (9.95). MS (ESI, m/z): 399 (M+, 100%). Exact mass calculated (found) for [M+H]+, m/z): 399.2659 (399.2671).

Workup

  1. stirringthe reaction stirred
  2. temperatureat reflux for 4 hours
  3. washthe mixture washed with water and brine
  4. customThe organic layer was collected
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customto yield a liquid

Sources & evidence

ORD record
ord-b59fd46b85744e24ab8615586cc05a99
Source dataset
uspto-grants-2014_09
Patent number
US08846978B2

Reaction notes

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