Xenon fluorides permit the controlled addition of fluorine across an olefinic double bond. They provide a series of fluorinating agents that permit ready separation from the product at a high purity. The reactions may be carried out in the vapor phase

Chernick, C. L.

Shieh, T. C.

Yang, N. C.

English

NASA Technical Reports Server

June 1967
	 Brief 67-10185 
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H 
AEC-NASA Tech Briefs describe innovations resulting from the research and development program 
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the Clearinghouse for Federal Scientific and Technical Information, Springfield, Virginia 22151. 
Xenon Fluorides Show Potential as Fluorinating Agents 
The problem: 
To devise a straightforward method for the con-
trolled addition of fluorine across an olefinic double 
bond. The method should also permit ready separa-
tion of the product from the reduced fluorinating agent 
at a high purity. Present methods using elemental 
fluorine or metal fluorides for fluorinating olefins have 
a number of disadvantages in that the reactions are 
somewhat difficult to carry out and are often accom-
panied by fluorine substitution, cleavage of the double 
bond, or both. 
The solution: 
Xenon fluorides provide a series of fluorinating 
agents which appear attractive for controllable selec-
tive fluorinations yielding high purity products. They 
form elemental xenon as the only byproduct, and this 
is readily separable from the organic products. In 
addition, the reactions may be carried out in the vapor 
phase at room temperature, eliminating the problems 
associated with the use of solvents. 
How it's done: 
The use of xenon fluorides to effect fluorine addi-
tion to unsaturated organic molecules has been investi-
gated at Argonne National Laboratory. The apparatus 
used in these investigations is similar to that used in 
the preparation of xenon fluorides, being constructed 
mainly of nickel or monel. Purified reactants were 
condensed at the temperature of liquid nitrogen 
(-195°) into a 130-cc nickel can which could be 
weighed. The can was allowed to warm to room 
temperature and the course of the reaction followed 
by observing the change of pressure in the can. It was 
assumed that the reaction had reached completion 
when no further pressure change was observed. The 
This document was prepared under the sponsorship of the Atomic 
Energy Commission and/or the National Aeronautics and Space 
Administration. Neither the United States Government nor any per-
son acting on behalf of the United States Government assumes any
reaction products were separated by trapping out 
components at differing temperatures and the various 
components were identified by their infrared, nuclear 
magnetic resonance, and/or mass spectra. 
As an example of this type of reaction, 0.75 milli-
mole of XeF4 and 1.28 millimoles of perfluoropropene 
were allowed to stand in a nickel can at room tem-
perature for 15 hours, after which the pressure was 
found to be constant. The mixture was cooled in a 
dry ice—trichloroethylene bath at —78° and the vola-
tile material removed by pumping through a trap at 
—195°. The material collected was shown to contain 
only xenon and perfluoropropane, and the material 
remaining in the reaction vessel was found to be un-
reacted xenon tetrafluoride. 
XeF4 + 2CF3CF=CF2—+2CF3CF2CF3 + Xe 
Under similar conditions XeF 6 , which is more re-
active than XeF4, reacts with perfluoropropane to give 
both C2F6 and CF4 as the major products. A mixture 
of XeF, which is less reactive than XeF 4, and per-
fluoropropene does not react even after 6 days. This 
suggests that XeF2 is not an intermediate in these 
fluorinating reactions. 
In additional investigations, it was shown that both 
xenon difluoride and xenon tetrafluoride react with 
ethylene at room temperature to give quantitative 
yields of 1:1 and 1:2 difluoroethane (CH2FCH2F) 
and elemental xenon. 
Notes: 
1. These investigations indicate that xenon fluorides 
have a considerable potential as fluorinating agents 
in organic chemistry, especially in small scale re-
actions where precise control and a high purity 
product are of importance.
(continued overleaf) 
liability resulting from the use of the information contained in this 
document, or warrants that the use of any information, apparatus, 
method, or process disclosed in this document may not infringe pri-
vately owned rights.
https://ntrs.nasa.gov/search.jsp?R=19670000185 2020-03-11T20:50:46+00:00Z
Additional details are contained in: Journal of 
the American Chemical Society, vol. 86, reference 
5021 (1964). 
Inquiries concerning this innovation may be di-
rected to:
Office of Industrial Cooperation 
Argonne National Laboratory 
9700 South Cass Avenue 
Argonne, Illinois 60439 
Reference: B67-10185 
Source: T. C. Shieh, N. C. Yang, and C. L. Chernick

Chemistry Division
(ARG-113)
Patent status: 
Inquiries about obtaining rights for commercial use 
of this innovation may be made to: 
Mr. George H. Lee, Chief 
Chicago Patent Group 
U.S. Atomic Energy Commission 
Chicago Operations Office 
9800 South Cass Avenue 
Argonne, Illinois 60439 
Brief 67-10185
	 Category 03


Xenon fluorides show potential as fluorinating agents

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