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Synthetic Communications
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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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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
sodium dialkyl phosphite and chlorodifluororethane, but this mode of preparation of phoaphonates is specific for the difluoromethyl
72
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-
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.
73
fluoromethylphosphonate involved transferring tributyl phosphite (25 g, 100 mmol) that was freshly distilled over sodium into a 75 The
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 "
9 -61.8, Jp-p
external reference) showed a triplet at 6 -0.8 ppm. H-decoupled) was a pentet of triplets, JP-H 7.3 Hz.
31P (non
thick valled Pyrex glass tube i n an anhydrous atmosphere box. Into the tube that was evacuated at -196
OC,
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
cooled to -196OC and the C2H5I and any unreacted CF3I were
74
distilled away.
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
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