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Synthetic Communications
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Simple Preparation of Dialkyl Polyfluoroalkyl Phosphonates


Tariq Mahmood & Jean'Ne M. Shreeve
a a a

Department of Chemistry, University of Idaho, Moscow, ID, 83843 Available online: 05 Dec 2006

To cite this article: Tariq Mahmood & Jean'Ne M. Shreeve (1987): Simple Preparation of Dialkyl Polyfluoroalkyl Phosphonates, Synthetic Communications, 17:1, 71-75 To link to this article: http://dx.doi.org/10.1080/00397918708063904

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SYNTHETIC COMMUNICATIONS, 17(1), 71-75 (1987)

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SIMPLE PREPARATION OF DIALKYL POLYFLUOROALKYL PHOSPHONATES Tariq Mahmood and Jean'ne H. Shreew* Department of Chemistry, University of Idaho MOSCOW, ID 83843 Several dialkyl polyfluoroalkyl phosphonates can be prepared by reacting trialkyl phosphites with trifluoromethyl iodide or dibromodifluoromethane under pressure andtor photolytic conditions. The resulting phosphonates are useful precursors to the corresponding phosphonic acids.

Dialkyl polyfluoroalkyl phosphonates are useful precursors to the corresponding phosphonic acids or to a wide variety of derivatives due to the several sites in the molecules which are subject to attack. The oxidative hydrolysis of trifluoro-

methylphosphinic derivatives gave the trifluoromethyl phosphorous, phosphonic, and phosphinic acids. 4-7 Later the infrared spectrum of diethyl trifluoromethylphosphonate was reported, of its preparation were not given.

* but details

The closely related esters of

difluoroaethylphosphonic acids were prepared by the reaction of

sodium dialkyl phosphite and chlorodifluororethane, but this mode of preparation of phoaphonates is specific for the difluoromethyl

To vhoa correspondence should be addressed.


71

Copyright0 1987 by Marcel Dekker, Inc.

72

MAHMOOD AND SHREEVE

Dibutyl moiety only and ie not of general a p p l i ~ a b i l i t y . ~ bromodifluorooethylphoephonate resulted from refluxing dibromodifluoromethane with tributyl phosphite. lo Photolyeie of tri-

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fluoromethyl iodide with triethylphoephite formed diethyl(trif1uoromethyl)phoephonate in 51% yield. 1 1 Chlorination of

F3CP(OR)2 followed by treatment with ROH resulted in several dialkyl trifluoromethyl phoephonates in yielde ranging between 41-49%. 12 We report here a faet, eimple and eseentially quantitative route to dialkyl trifluoromethyl or monohalodifluoromethylphoaphonatee by the reaction of the appropriate trialkyl phosphite and

monohalotrifluoromethane or dihalodifluoromethane.

The reaction

was carried out in a metal or Pyrex glees preesure veeeel without the addition of a eolvent and led eeeentially quantitatively to the correeponding phoephonatee. These are iaolated ae nonvolatile

liquids that remained in the reaction veseele after the other volatile producte were removed under vacuum. (n-C4Hg0)3P t CF2Br2

250 36 , h
etainleee steel

(n-C4Hg0)2P(O)CF2Br

(C2H50)3P t CF3I

t n-CqHgBr

100%

48 , h

(C2H50)2P(O)CP3

Pyrex

C2H5I

100%

Thie method ie euperior to those deecribed becauee of the eaee of handling the volatile halofluoromethanes using vacuum line techniques and the fact that the product yielde are doubled. Purity of the products was very high baaed on 19P and 31P NHR spectral analyeia.

DIALKYL POLYFLUOROALKYL PHOSPHONATES


A typical procedure for the synthesis of dibutyl bromodi-

73

fluoromethylphosphonate involved transferring tributyl phosphite (25 g, 100 mmol) that was freshly distilled over sodium into a 75 The

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ml stainless steel reactor in an anhydrous atmosphere box.

reactor was closed with a valve, was cooled to -196 OC, and was evacuated.
To the cooled reactor was transferred 23.1 g (110

mmol) of CF2Br2. The reaction was allowed to warm to 25 O C and was agitated for 36 hr. After the volatile materials (n-C&Br and

any unreacted CF2Br2) were removed, dibutyl bromodifluoromethylphosphonate remained behind in the reactor as a nonvolatile liquid in approximately quantitative yield.
R spectrum (in The 19F "

cDCl3 with CFC13 as external reference) consisted of a doublet at

9 -61.8, Jp-p

92.8 Hz, and 31P{H} (in CDCl3 with H3P04 as

external reference) showed a triplet at 6 -0.8 ppm. H-decoupled) was a pentet of triplets, JP-H 7.3 Hz.

31P (non

A typical procedure for the synthesis of diethyl trifluoro-

methylphosphonate required transferring


g, 58 -01)

triethyl phosphite (9.65

which has been freshly distilled over sodium into a

thick valled Pyrex glass tube i n an anhydrous atmosphere box. Into the tube that was evacuated at -196
OC,

CF3I (23.6 g, 116 The glass

w o l ) was condensed, and the tube sealed off with care.

seal must be done carefully to avoid leaving a weak point in the tube wall. The tube was allowed to warm to 25OC and then exposed The tube was

to UV radiation (Hanovia Utility lamp) for 48 hr.

cooled to -196OC and the C2H5I and any unreacted CF3I were

74
distilled away.

MAHMOOD AND SHREEVE The nonvolatile liquid diethyl trifluoromethyl-

phosphonate remained in the Pyrex tube in

100% yield. The 19F

NMR spectrum (in cDCl3, with CFC13 as external reference) con-

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sisted of a doublet at 9 -72.2, JP-F = 122.1 Hz, and 31P{H} (in CDCl3 with H3PO4 as external reference) showed a quartet centered at 8 -3.4 QQm. ACKNOWLEDGMENT Acknowledgment is expressed to the donors of the Petroleum Research Fund administered by the American Chemical Society
to the Gas Research Institute for support of this research.

and
We

thank Dr. Gary Knerr for mass spectral data.

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