Iodide Ion → (3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)phosphonic acid diethyl ester

HRID 1952413Notes

Reaction equation

HRID 1952413 reaction equation
[F:1][C:2]([F:22])([C:6]([F:21])([F:20])[C:7]([F:19])([F:18])[C:8]([F:17])([F:16])[C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])[CH2:3][CH2:4]I.[P:23]([O:30][CH2:31][CH3:32])([O:27][CH2:28][CH3:29])[O:24]CC.[I-]>>[CH2:31]([O:30][P:23]([CH2:4][CH2:3][C:2]([F:1])([F:22])[C:6]([F:20])([F:21])[C:7]([F:18])([F:19])[C:8]([F:16])([F:17])[C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])(=[O:24])[O:27][CH2:28][CH3:29])[CH3:32]

Participants

4

Reactant 3

HCID 30165Iodide IonHCID 31215Triethyl phosphiteHCID 748881,1,1,2,2,3,3,4,4,5,5,6,6-Tridecafluoro-8-iodooctane

Product 1

HCID 11070933(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)phosphonic acid diethyl ester

Procedure

3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoro-1-iodooctane (5.68 g, 11.98 mmol) and P(OEt)3 (4 ml, excess) were placed in a 50 ml RBF fitted with a reflux condenser. The mixture was subjected to microwave irradiation (300 W) for 2 hours (max. temp ca. 155° C.) after which time the starting iodide was no longer visible by TLC. 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 elution) afforded the desired product as a thick pale yellow oil. Yield 3.71 g, 64%. Analysis found (calculated) %: C, 29.25 (29.77); H, 2.96 (2.91). 1H NMR (CDCl3, 400 MHz, 298 K): δ 4.11 (m, 4H), 2.36 (m, 2H), 1.98 (m, 2H), 1.33 (t, J=7 Hz). 13C{1H} NMR (CDCl3, 100 MHz, 298 K): δ 121-105 (m, C-F coupling unresolved), 62.18 (d, JC-P=6 Hz), 25.15 (t, JC-F=24 Hz), 17.10 (d of t, JC-P=148 Hz, JC-F=4 Hz), 16.34 (d, JC-P=6 Hz). 31P{1H} NMR (CDCl3, 162 MHz, 298 K): δ 28.96. MS (FAB, m/z): 485 ([M+H]+, 100%). Exact mass found (calculated for [M+H]+, m/z): 485.05499 (485.05513).

Workup

  1. customRBF fitted with a reflux condenser
  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 elution)

Sources & evidence

ORD record
ord-cebcc36ea49c4a4db3cb8b577ac12959
Source dataset
uspto-grants-2013_03
Patent number
US08405069B2

Reaction notes

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