Triethyl phosphite → 1-[2-(2-Diethoxyphosphorylethoxy)ethoxy]-2-methoxy-ethane

HRID 1952415Notes

Reaction equation

HRID 1952415 reaction equation
[CH3:1][O:2][CH2:3][CH2:4][O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10]I.[P:12]([O:19]CC)([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15]>O1CCOCC1>[CH2:14]([O:13][P:12]([CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][CH2:4][CH2:3][O:2][CH3:1])(=[O:19])[O:16][CH2:17][CH3:18])[CH3:15]

Participants

4

Reactant 2

HCID 31215Triethyl phosphiteHCID 106360201-Iodo-3,6,9-trioxadecane

Product 1

HCID 866385191-[2-(2-Diethoxyphosphorylethoxy)ethoxy]-2-methoxy-ethane

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

{2-[2-(2-Methoxyethoxy)ethoxy]ethyl}iodide (6.64 g, 24.3 mmol) and P(OEt)3 (4.22 ml, 24.3 mmol) were dissolved in 1,4-dioxane (30 ml) and stirred under reflux for 24 hours. Volatiles were distilled in vacuo (150° C., 0.01 torr) to give the crude material as a thick yellow oil. Column chromatography (silica gel, EtOAc:MeOH 95:5 elution) afforded the desired product as a pale yellow oil. Yield 1.0 g, 15%. Alternative synthesis using {2-[2-(2-Methoxyethoxy)ethoxy]ethyl}iodide (5.00 g, 18.2 mmol) and P(OEt)3 (10 ml, excess) under microwave irradiation (100 W, 1 hr) gave higher yield after column chromatography (3.06 g, 10.7 mmol, 59%). 1H NMR (CDCl3, 400 MHz, 298 K): δ 4.08 (m, 4H), 3.67 (d of t, JH-P=10 Hz, JH-H=7 Hz, 2H), 3.60 (m, 6H), 3.50 (m, 2H), 3.36 (s, 3H), 2.09 (d of t, JH-P=20 Hz, JH-H=7 Hz, 2H), 1.28 (t, J=7 Hz). 13C {1H} NMR (CDCl3, 100 MHz, 298 K): δ 71.72, 70.35, 70.30, 69.97, 64.92, 61.44 (d, JC-P=6 Hz), 58.82, 26.77 (d, JC-P=138 Hz), 16.22 (d, JC-P=6 Hz). 31P{1H} NMR (CDCl3, 162 MHz, 298 K): δ 29.23. MS (FAB, m/z): 285 ([M+H]+, 100%). Exact mass found (calculated for [M+H]+, m/z): 285.15395 (285.14670).

Workup

  1. temperatureunder reflux for 24 hours
  2. distillationVolatiles were distilled in vacuo (150° C., 0.01 torr)
  3. customto give the crude material as a thick yellow oil
  4. washColumn chromatography (silica gel, EtOAc:MeOH 95:5 elution)

Sources & evidence

ORD record
ord-b95cce8c7b0547fbb3284d6faf359831
Source dataset
uspto-grants-2013_03
Patent number
US08405069B2

Reaction notes

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