Reactions of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone with various amines

Article abstract of DOI:10.1016/j.jfluchem.2007.10.006

The reaction of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone, perfluoroethyl perfluoroisopropyl, or bis-perfluoroisopropyl ketone with various amines has been studied and the products identified. A comparison of the reactivity of the ketones with different amines is made and identified by mass spectroscopy. The reaction of diethyl amine with all three ketones leads to two unexpected products and the mechanism of their formation is considered.

Full text of DOI:10.1016/j.jfluchem.2007.10.006

Available online at www.sciencedirect.com
Journal of Fluorine Chemistry 129 (2008) 178–184
www.elsevier.com/locate/fluor
Reactions of poly(hexafluoropropylene oxide) perfluoroisopropyl
ketone with various amines
a,
a
a
Jon L. Howell b, , Chadron M. Friesen , Krista L. Laugesen , Alice E. van der Ende
*
*
a Trinity Western University, Department of Chemistry, 7600 Glover Road, Langley, BC V2Y 1Y1, Canada
b E. I. du Pont de Nemours, Experimental Station, Building 402, Room 4332C, Rt 141 Henry & Clay Works, Wilmington, DE 19880-0402, USA
Received 1 August 2007; received in revised form 26 October 2007; accepted 28 October 2007
Available online 4 November 2007
Abstract
The reaction of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone, perfluoroethyl perfluoroisopropyl, or bis-perfluoroisopropyl
ketone with various amines has been studied and the products identified. A comparison of the reactivity of the ketones with different amines is made
and identified by mass spectroscopy. The reaction of diethyl amine with all three ketones leads to two unexpected products and the mechanism of
their formation is considered.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Poly(hexafluoropropylene oxide); Fluorinated ketones; Amines
1. Introduction
fluorinated hemiaminal is a stable species, its dehydration to the
imine does not occur readily. However, it is possible to induce
the hemiaminal to dehydrate. Middleton and Krespan outlined a
synthesis that takes advantage of the relative acidity of the
hydroxyl group whereby pyridine is added (see Scheme 2) to
remove the hydroxyl proton and POCl3 is added to bring about
the dehydration [6].
Poly(hexafluoropropylene oxide), poly(HFPO), is a member
of an important class of compounds, perfluoropolyethers
(PFPEs), which function as thermally and chemically stable
lubricants, greases and fluids for corrosive environments. Since
the polymer was first reported in the 1960s [1,2] many
modifications have been made to the acyl fluoride terminated
intermediate, opening up a wide variety of new chemistries.
Among the possible terminal groups observed in poly(-
HFPO) is a perfluoroketone, for example poly(HFPO)
perfluoroisopropyl ketone. This ketone can be manufactured
(see Scheme 1) through the reaction of poly(HFPO) acid
fluoride with hexafluoropropylene (HFP) in the presence of a
suitable catalyst such as cesium fluoride [3,4].
Although fluorinated hemiaminals are relatively stable, it
has been reported that over long periods of time they
decompose into an amide and a hydrofluorocarbon [5]. Heat
(see Scheme 3) accelerates the decomposition [6].
Hexafluoroacetone has been the focus of the majority of the
reported studies between fluorinated ketones and amines.
However, when either trifluoromethyl group of the hexafluor-
oacetone is replaced with a branched perfluorinated moiety,
alternative chemistries ensue. Smith, Fawcett and Coffman
outline the synthesis of branched bis-(perfluoroisopropyl)
ketone [3]. They report that with the addition of nucleophilic
reagents such as ammonia the ketone immediately cleaves into
2-hydroheptafluoropropane and perfluoroisobutanamide.
Lindner and Lemal discuss the effect of steric bulk on the
stability of various hydrates and hemiketals of highly
fluorinated ketones [7]. They found that as the steric crowding
was reduced, the hydrate or hemiketal became more stable. We
thought that this trend seen in the addition of water or alcohol to
a fluoroketone might extend to addition of amines.
Simple fluorinated ketones such as hexafluoroacetone, add
to nucleophiles such as amines easily. The intermediate
hemiaminal is more stable than its alkyl counterpart and
the equilibrium favors its formation [5,6]. This is, in part, due to
the increased positive charge on the carbonyl group caused by
the electron withdrawing effect of the fluorine atoms. As the
* Corresponding authors.
E-mail addresses: jon.l.howell@usa.dupont.com (J.L. Howell),
chad.friesen@twu.ca (C.M. Friesen).
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.10.006

J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
179
Scheme 3. Decomposition of a hemiaminal into a fluoroalkane and a fluor-
oamide.
2. Results
2.1. Reactions of methyl ester with amines (pyrrolidine, n-
butyl, and diethylamine)
Scheme 1. Formation of poly(hexafluoropropylene oxide)perfluoroisopropyl
ketone.
The poly(HFPO) methyl ester was shown to produce
poly(HFPO)-based amides in the presence of pyrrolidine and n-
butylamine: F(CF(CF3)CF2O)3CF(CF3)-C(O)N(CH2)3CH3 and
F(CF(CF3)CF2O)3CF(CF3)C(O)NHC4H9, respectively. How-
ever, when mixed with diethylamine, the methyl ester
decomposes to F(CF(CF3)CF2O)3CFHCF3. The decomposition
of the methyl ester is highly unusual, however not without
precedence [9].
2.2. Perfluoroethylisopropyl ketone reactions with amines
(n-butyl, pyrrolidine, and diethylamine)
Scheme 2. Formation of the imine of a fluorinated ketone using base and
POCl3.
The reactions of the least sterically hindered perfluoroketone
of this study with amines resulted in ketone decomposition, and
did not form a hemiaminal. The reaction of the perfluoroethy-
lisopropyl with n-butylamine and pyrrolidine, produced CF3
CFHCF3 and the corresponding amide CF3CF2C(O)NH(CH2)3
CH3 and CF3CF2C(O)NC4H8, respectively. In the case of
diethylamine, the reaction proceeded much more slowly, taking
a few days to go to completion. As in the case for the other
amines, (CF3)2CFH is found, but additionally, RfC(O)NHCH2
CH3 and RfC(O)CH CHN(CH2CH3)2 (where Rf = CF3CF2–)
are formed.
Poly(HFPO) perfluoroisopropyl ketone is highly hindered
so its reactions with amines might be expected to react in a
fashion similar to bis-(perfluoroisopropyl) ketone. The
reactions of poly(HFPO) ketone with various amines were
conducted to see how they compare to fluorinated ketones in
the literature. Additionally, the same reactions were carried out
with both a linear-branched and a bis-branched ketone,
perfluoroethylisopropyl ketone and perfluorobis-isopropyl
ketone, respectively.
Since the reaction between poly(HFPO)methyl esters and
amines are known [8], a sample of poly(HFPO) methyl ester
(F(CF(CF3)CF2O)3CF(CF3)C(O)OCH3) was reacted with n-
butylamine, pyrrolidine, and diethylamine. A study of these
reaction products should provide an insight to the chemistries
obtained from the reactions of the same amines with
poly(HFPO) perfluoroisopropyl ketone.
2.3. Perfluorobis-isopropyl ketone reactions with amines
(n-butyl, pyrrolidine, and diethylamine)
Similar to perfluoroethylisopropyl ketone, the perfluorobis-
isopropyl did not form the hemiaminal. The reaction of
the perfluorobis-isopropyl with n-butylamine and pyrro-
lidine produced CF3CFHCF3 and the corresponding amides
(CF3)2CFC(O)NH(CH2)3CH3 and (CF3)2CFC(O)NC4H8),
Table 1 shows a summary of spectral and physical
characterization of the starting reactants and Scheme 4 shows
their synthesis.
Table 1
Starting material general characteristics
Ethylisopropylketone
Bisisopropyl ketone
Poly(HFPO)4 isopropyl ketone
Poly(HFPO) methyl ester
MW
316
317 (M + H+)
366
367 (M + H+)
814
676
CI (MS)
EI (MS)
463 (M À 2HFPO + F)
147, 169, 197
N/A
69, 119, 197
69, 169, 197
59, 131, 169
19F NMR
(CF3)2CF–
À192.4
À75.6
À83.8
À122.4 (d)
–
À189.8
À190.2
À75.1,
–
–
(CF3)2CF–
CF3CF2–
À75.2
À75.4
–
–
–
–
CF3CF2–
–
–
CF3CF2CF2O–
À146.0
À146.0

180
J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
Scheme 4. Formation of the perfluoroketone.
respectively. In the case of diethylamine, again the reaction
took several days and produced (CF3)2CFH, RfC(O)NHCH2
CH3 and RfC(O)CH CHN(CH2CH3)2 (where Rf = (CF3)2
CF–).
insipient negative charge on the leaving group and the amine
steric bulk. The evidence of the influence of the first factor can
be found in the products of the reaction of perfluorinated
ketones with the three amines. In all cases the CF3CFHCF3 is
the principal leaving group. We speculate the initial step in the
reaction is the formation of the non-isolatable thermally
unstable hemiaminal. The leaving perfluoroisopropyl better
stabilizes the forming carbanioic center and thus primarily
CF3CFHCF3 is observed. Another example of this effect is seen
in the reaction of poly(HFPO) methyl ester with diethylamine.
The product poly(HFPO)-CFHCF3, is formed due to the ability
of the poly(HFPO) segment to better stabilize the carbanioic
center than the methoxy group [9].
2.4. Poly(hexafluoropropylene oxide) perfluoroisopropyl
ketone reactions with amines (n-butyl, pyrrolidine, and
diethylamine)
The reactions of the poly(HFPO)perfluoroketone with n-
butylamine gave the primary products of (CF3)2CFH and
F[CF(CF3)CF2O]3 CF(CF3)C(O)NH(CH2)3CH3 with trace
amounts of (CF3)2CFC(O)NH(CH2)3CH3, F[CF(CF3)CF2O]3
CFHCF3, C3H7CH NC4H9 and poly(HFPO)nCF(CF3)-
C(O)NH2. The reaction with pyrrolidine produced (CF3)2CFH
and F[CF(CF3)CF2O]3CF(CF3)CONC4H8 with trace amounts
of (CF3)2CFCONC4H8, F(CF(CF3)CF2O)3CFHCF3 and a
speculated, non-isolated, oligomer of pyrrolidine. When the
poly(HFPO)perfluoroisopropyl ketone was reacted with diethy-
lamine F(CF(CF3)CF2O)3CFHCF3 was formed, along with
two products, F[CF(CF3)CF2O]3CF(CF3)C(O)NHCH2CH3 and
F[CF(CF3)CF2O]3CF(CF3)C(O)–CH CHNCH2CH3, respec-
tively. The hemiaminal did not form.
Thus, with the exception of diethyl amine, in the case of the
ketones and the methyl ester, the resulting co-products are the
perfluoroisobutanamide or the N-tetramethylene amide.
Another unusual finding in the case of the n-butylamine and
pyrrodine C3H7CH NC4H9 or what appears to be an oligomer
of pyrrolidine were observed, respectively. We suspect the
formation of the imine, C3H7CH NC4H9, follows the synthesis
found in Scheme 5. The polymer of pyrrolidine could be formed
in a similar manner. Unexpectedly, the amines appear to be in
an oxidizing atmosphere where the first intermediate must
be the simple imine. A reason for the imine formation could be
due to the electron-deficient carbonyl carbon attracting a
hydride from the amine, followed by a proton loss from the
nitrogen. This imine then further reacts with another equivalent
of amine leading to free ammonia and the alkyl-substituted
3. Discussion
The products from the reactions of perfluorinated ketones
with amines, are dictated by two factors; the formation of the
Scheme 5. Formation of imine using butyl amine.

J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
181
nucleophile and react with the various ketones to produce
the observed N,N-diethylaminoethylene perfluoroalkyl(ether)
ketone (Scheme 7).
While pyrrolidine and diethylamine have similar basicities
[10], the steric bulk of diethyl amine slows precipitously from a
few hours to a few days. This rate reduction allows time for the
secondary reaction of diethyl amine to form ethylamine and
N,N-diethylaminoethylene.
4. Conclusions
The original premise of the work was to prepare new
fluorinated imines from perfluorinated ketones. Although, no
new perfluoro imines were observed, a rich variety of
chemistries was observed in reacting different amines with
perfluoroisopropyl perfluoroketones. In each case the perfluor-
oisopropyl group is lost preferentially, the trend being branched
side chains are lost in preference to normal side chains and
perfluoroisopropyl in preference to poly(HFPO) (both
branched). In these reactions where excess amine is incorpo-
rated, enamines from imine–enamine tautomerism can form
and gives rise to perfluorinated vinyl ketone amines (see
Schemes 5–7).
Scheme 6. Formation of imine and enamine using diethyl amine.
imine. Evidence of free ammonia is observed in the case of the
poly(HFPO) perfluoroisopropyl ketone where the simple amide
(–C(O)NH2) was observed.
Unlike the reaction of the ketones with n-butylamine and
pyrrolidine, the products formed during the reaction of the
ketones with diethylamine are less intuitive. Instead of the
expected N,N-diethylamide, two unexpected compounds,
RfC(O)NHCH2CH3 and RfC(O)CH CHN(CH2CH3)2, are
found. It can be speculated that the formation of these
compounds arise from two new compounds, ethylamine and
N,N-diethylaminoethylene, created in the reaction mixture
(excess diethylamine). This reaction environment also appears
to be in an oxidative in nature. The genesis of these two new
compounds is outlined above in Scheme 6.
The reactions of the amines with poly(HFPO) methyl ester
to form the appropriate amide was helpful in understanding the
reactions of the amines with ketones. But in the case of
diethylamine only F[CF(CF3)CF2O]3CFHCF3 was observed.
Ethylamine, reacts like n-butylamine with methyl ester, or n-
butylamine with the various ketones producing the observed N-
ethylamide. The N,N-diethylaminoethylene can act as a
5. Experimental
General. All analysis were carried out using a 5890N Gas
Chromatograph with a 5973N Mass Selective Detector with
either CI (Methane) or EI detectors. The Gas Chromatograph
was equipped with a 30 m  0.250 mm, 0.25 mm df, DB-1
column. The initial temperature of 60 8C was held for 2 min
and then increased at 10 8C/min to 250 8C and held for 15 min.
A 1:50 split was used. Only those peaks characteristic of the
compound in question or high in intensity are reported for the
mass spectral data. The characteristic fragments of poly(HFPO)
+
+
+
+
are: 69 (CF3 ); 100 (C2F4 ); 119 (C2F5 ); 169 (CF3CF2CF2 ).
NMR analysis of some of the products was conducted on a
Bruker DRX 400 MHz spectrometer. The experimental
procedures for the reactions with n-butylamine, diethylamine,
and pyrrolidine are all similar so a generic procedure is given.
n-Butylamine, diethylamine and pyrrolide were purchased
from Aldrich and used as received.
5.1. Starting materials characterization
Perfluoroethylisopropyl ketone (CF3CF2C(O)CF(CF3)2.
GC/EI/MS (70 eV) retention time, m/z (fragment): 1.605 min,
+
+
+
69 (CF3 ), 100 (C2F4 ), 119 (CF3CF2 ), 147 (CF3CF2C(O)+),
169 ((CF3)2CF+), 197 ((CF3)2CFC(O)+) (see Fig. 1).
Perfluorobis-isopropyl ketone ((CF3)2CFC(O)CF(CF3)2.
GC/EI/MS (70 eV) retention time, m/z (fragment):
+
+
+
1.668 min, 69 (CF3 ), 100 (C2F4 ), 119 (CF3CF2 ), 169
((CF3)2CF+), 197 ((CF3)2CFC(O)+) (see Fig. 1).
Scheme 7. Formation of perfluoroalkyl(ether) N,N-diethylaminoethylene
ketone.

182
J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
Fig. 1. EI/MS of fluorinated ketones: (A) perfluoroethylisopropyl ketone and
(B) perfluorodiisopropyl ketone.
Fig. 2. EI/MS of poly(HFPO) derivatives: (A) MS of poly(HFPO) methyl ester
and (B) MS.
Poly(HFPO) perfluoroisopropyl ketone (F[CF(CF3)CF2]3
CF(CF3)C(O)-CF(CF3)2). The poly(HFPO) perfluoroisopro-
pyl ketone was obtained by adding cesium fluoride to
hexafluoropropene and then introducing the poly(HFPO) acid
fluoride. GC/EI/MS (70 eV) retention time, m/z (fragment):
3.936 min, 147 (C(CF3)CF2O+), 197 ((CF3)2CFC(O)+), 285
products of these reactions are (CF3)2CFH, C3H7CH NC4H9,
and the corresponding amide CF3CF2C(O)NH(CH2)3CH3.
C3H7CH NC4H9 (N-butylidene-1-butanamine) GC/EI/MS
(70 eV,) retention time, m/z (fragment): 8.604 min, 42 (CH3
(CF3CF2CF2OCF(CF3)+), 335 (CF3CF2CF2OCF(CF3)CF2 ),
+
+
463 (CF(CF3)CF2OCF(CF3)–C(O)CF(CF3)2 ) (see Fig. 2).
+
Poly(HFPO) methyl ester ((F[CF(CF3)CF2]nCF(CF3)
C(O)OCH3). where n = 4, 5, 6. The poly(HFPO) methyl ester
was made from a low molecular weight cut of poly(HFPO) acid
fluoride, where n = 4, 5, 6, by methanolysis of the acyl fluoride.
GC/EI/MS (70 eV) retention time, m/z (fragment):
CH2CH+); 56 (CH3CH2CH2CH+); 57 (CH3CH2CH2CH2 ); 70
(CH3CH2CH2CH N+); 84 (CH3CH2CH2CH NCH2 ); 99
+
(CH3CH2CH2CH NCH2-CH2+ + H+); 112 (CH3CH2–CH2
+
CH NCH2CH2CH2 ); 126 (CH3CH2CH2CH NCH2CH2–
+
CH2CH3 À H+).
+
6.447 min, 59 (C(O)CH3 ), 131 (CF3CF2C+), 150 (CF3CF2
CF3CFHCF3. GC/EI/MS (70 eV,) retention time, m/z
CF+, 27), 325 (CF(CF3)CF2OCF(CF3)–C(O)OCH3 ) (see
(fragment): 1.513 min, 69 (CF3 ); 82 (CF3CH+); 101 (CF3
+
+
Fig. 2).
CFH+); 151 ((CF3)2CF + H+). 19F NMR (376 MHz; CF2
ClCFCl2) d (ppm): 7.62 (dm, 1H, JH2F = 45 Hz and JH3F = 6 Hz).
C2F5C(O)NHC4H9. GC/CI(methane)/MS (70 eV,) retention
time, m/z (fragment): 8.043 min, 41 (C2H3N+), 100 (H9C4
General procedure. Approximately, 0.25 g of the starting
material was added to a 2 mL GC sample vial at room
temperature. 0.75 g of Freon 11 (CFCl3) was added to the vial.
The vial was shaken. A fivefold molar excess of the amine was
added to the vial, carefully so as not to mix the two layers. The
vial was capped and then shaken. The reaction is exothermic in
the case with n-butylamine and pyrrolidine. The contents of the
vial were analyzed by GC/MS within 3–5 min of shaking.
Further analysis by GC/MS was done until the reaction came to
completion.
+
HNC(O)+); 119 (C2F5 ); 177 (C2F5C(O)NHCH2+ + H+); 190
+
(C2F5C(O)NHCH2CH2 ); 220 (M + H+).
5.2.2. Reaction of the perfluorobis-isopropyl ketone with n-
butylamine
The reaction between the ketone and n-butylamine goes to
completion immediately and is exothermic. The primary
products of these reactions are (CF3)2CFH, C3H7CH NC4
H9, and the corresponding amide (CF3)2CFC(O)–NH(CH2)3
CH3.
5.2. Reactions of perfluoro ketones with n-butylamine
5.2.1. Reaction of the perfluoroethylisopropyl ketone with
n-butylamine
(CF3)2CFC(O)NH(CH2)3CH3. GC/CI(Methane)/MS (70
eV,) retention time, m/z (fragment): 8.056 min, 41 (C2H3N+),
+
57 (C4H9 ); 71 (NC4H9 ); 100 (C(O)NHC4H9 ); 169 (C3F7 );
+
+
+
The reaction between the ketone and n-butylamine goes to
completion immediately and is exothermic. The primary
250 (M À F); 270 (M + H+).

J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
183
5.2.3. Reaction of poly(HFPO) methyl ester with n-
butylamine
of these reactions are (CF3)2CFH, and the corresponding amide
(CF3)2CFC(O)NH(CH2)3CH3.
Reaction with n-butylamine causes the poly(HFPO) methyl
ester to immediately decompose into Hydrogen-Endcap (1.851
and 2.530 min) and N-n-butylpoly(HFPO) amide (10.355,
12.041 and 13.464 min). A small peak due to N-butylidene-1-
butanamine (8.157 min) is also present.
(CF3)2CFC(O)NC4H8 (N-tetramethyleneperfluoroisobuta-
namide). GC/CI(Methane) /MS (70 eV,) retention time, m/z
+
(fragment): 9.624 min, 98 (C(O)NC4H8 ); 198 (CF2CF2
+
C(O)NC4H8 ); 248 (M À F); 268 (M + H+).
F(HFPO)3CF(CF3)C(O)NHC4H9. GC/CI(Methane)/MS
(70 eV,) retention time, m/z (fragment): 12.041 min, 41 (C2
5.3.3. Reaction of poly(HFPO) methyl ester with
pyrrolidine
H3N+), 57 (C4H9 ); 100 (H9C4HNC(O)+); 200 (H9C4HNC(O)
The reaction with pyrrolidine causes the poly(HFPO)
methyl ester to immediately decompose into Hydrogen-
Endcap (min) and N-tetramethylenepoly(HFPO)amide
(13.265 min).
+
CF(CF3)+); 366 (C4H9NHC(O)CF(CF3)OCF2CF(CF3)+); 432
+
(C4H9NHC(O)CF(CF3)OCF2CF(CF3)OCF2 ); 532 (C4H9NHC
(O)CF(CF3)OCF2CF–(CF3)OCF2CF(CF3)+); 598 (C4H9NH–
+
C(O)CF(CF3)OCF2CF(CF3)OCF2CF(CF3)OCF2 ).
F(HFPO)3CF(CF3)C(O)NC4H8. GC/CI(Methane)/MS (70
+
eV,) retention time, m/z (fragment): 13.265 min, 55 (C4H7 ); 98
+
(C(O)NC4H8 ); 198 ((CF3)2CFC(O)NC4H8 ); 264 (CF2
+
5.2.4. Reaction of the poly(HFPO) perfluoroisopropyl
ketone with n-butylamine
+
OCF(CF3)C(O)NC4H8 ); 364 (CF(CF3)CF2OCF(CF3)C(O)
+
NC4H8 ); 430 (CF2O–CF(CF3)CF2OCF(CF3)C(O)NC4H8 );
+
The reaction between the ketone and n-butylamine goes to
completion immediately and is exothermic. The primary
products of these reactions are (CF3)2CFH, C3H7CH NC4H9,
F[CF(CF3)CF2–O]nCF(CF3)C(O)NH(CH2)3CH3. Over time
F[CF(CF3)CF2O]nCFHCF3, and the corresponding amide
(CF3)2CFC(O)NH(CH2)3CH3 are produced.
+
530 ((CF(CF3)CF2O)2CF(CF3)C(O)NC4H8 ); 596 (CF2O(CF
+
(CF3)CF2O)2CF(CF3)C(O)NC4H8 ).
5.3.4. Reaction of the poly(HFPO) perfluoroisopropyl
ketone with pyrrolidine
F(HFPO)3CF(CF3)C(O)NHC4H9 (N-n-butylpoly(HFPO)
amide). GC/CI(Methane)/MS (70 eV,) retention time, m/z
The reaction with pyrrolidine is exothermic imme-
diately reacting with the ketone within seconds. The
primary products of these reactions are (CF3)2CFH, and
the corresponding amide F[CF(CF3)CF2O]3CF(CF3)C(O)
NHC4H8.
(fragment): 12.056 min, 41 (C2H3N+), 57 (C4H9 ); 69
+
+
+
+
(CF3 ); 100 (C(O)NHC4H9 ); 169 (CF3CF2CF2 ); 200 (H9C4
HN–C(O)CF(CF3)+); 366 (C4H9NHC(O)CF(CF3)OCF2CF
+
(CF3)+); 432 (C4H9NHC(O)–CF(CF3)OCF2CF(CF3)–OCF2 );
F(HFPO)3CF(CF3)C(O)NC4H8 (N-tetramethylenepoly(HF-
PO)amide). GC/CI (Methane)/MS (70 eV,) retention time, m/z
532 (C4H9NHC(O)CF(CF3)OCF2CF(CF3)OCF2CF–(CF3)+);
598 (C4H9NHC(O)–CF(CF3)OCF2CF(CF3)OCF2CF(CF3)
+
(fragment): 13.216 min, 69 (CF3 ); 98 (C(O)NC4H8 );
+
+
OCF2 ).
+
198 ((CF3)2CFC(O)NC4H8 ); 264 (CF2OCF(CF3)C(O)NC4
+
+
H8 ); 364 (CF(CF3)CF2OCF–(CF3)C(O)NC4H8 ); 430 (CF2
F(HFPO)3CFHCF3 (Hydrogen-Endcap). GC/CI(Methane)/
MS (70 eV,) retention time, m/z (fragment): 2.500 min, 69
+
OCF(CF3)CF2OCF(CF3)C(O)NC4H8 ); 530 ((CF(CF3)–CF2
+
(CF3 , 100), 100 (C2F4 , 21), 101 (CFHCF3 ); 119 (CF3CF2 );
+
+
+
O)2CF(CF3)C(O)NC4H8+); 596 (CF2O(CF(CF3)CF2O)2
CF(CF3)C(O)–NC4H8+); 696 ((CF(CF3)CF2)3CF(CF3)
+
147 (C(CF3)CF2O+); 169 (CF3CF2–CF2 ); 267 (CF(CF3)
+
CF2OCFHCF3 ); 335 (CF3CF2CF2OCF(CF3)CF2 ); 433 ((CF
+
+
C(O)NC4H8 ).
+
(CF3)–CF2O)2CFHCF3 ); 501 (CF3CF2CF2O–CF(CF3)CF2
+
OCF(CF3)CF2 ); 599 (CF3CF2CF2O(CF(CF3)CF2O)2CFHCF3
5.4. Reactions of perfluoro ketones with diethylamine
+ H+–HF).
5.4.1. Reaction of the perfluoroethylisopropyl ketone with
diethylamine
5.3. Reactions of perfluoro ketones with pyrrolidine
Diethylamine reacts relatively slowly with the ketone,
taking a few days to go to completion. The primary
products of these reactions are (CF3)2CFH, CF3CF2
C(O)NHCH2CH3, CF3CF2C(O)N(CH2CH3)2 and CF3CF2
C(O)CH CHNEt2.
5.3.1. Reaction of the perfluoroethylisopropyl ketone with
pyrrolidine
The reaction with pyrrolidine is exothermic immediately
reacting with the ketone within seconds. The primary products
of these reactions are (CF3)2CFH, and the corresponding amide
CF3CF2C(O)NH(CH2)3CH3.
CF3CF2C(O)NHC2H5. GC/CI(Methane)/MS (70 eV,)
retention time, m/z (fragment): 4.756 min, 41 (C2H3N+), 72
(H5C2HNC(O)+); 172 (M À F); 192 (M + H+).
C2F5C(O)NC4H8 (N-tetramethyleneperfluoropropanamide).
GC/CI(Methane)/MS (70 eV,) retention time, m/z (fragment):
C2F5C(O)N(C2H5)2. GC/CI(Methane)/MS (70 eV,) reten-
tion time, m/z (fragment): 7.126 min MS (CI) (m/z): 41
(C2H3N+), 100(Et2NC(O)+); 200 (M À F); 220 (M + H+)
trans-C2F5C(O)CH CHN(C2H5)2. GC/CI(Methane)/MS
(70 eV,) retention time, m/z (fragment): 14.669 min, 41
(C2H3N+), 126 ((Et)2NCH CHC(O)+); 226 (M À F); 246
(M + H+); 274 (M + H+ + 29).
+
9.824 min, 98 (C(O)NC4H8 ); 198 (M À F); 218 (M + H+).
5.3.2. Reaction of the perfluorobis-isopropyl ketone with
pyrrolidine
The reaction with pyrrolidine is exothermic immediately
reacting with the ketone within seconds. The primary products

184
J.L. Howell et al. / Journal of Fluorine Chemistry 129 (2008) 178–184
5.4.2. Reaction of the perfluorobis-isopropyl ketone with
diethylamine
trans-F(HFPO)3CF(CF3)C(O)CH CHN(Et)2.
GC/
CI(Methane)/MS (70 eV,) retention time, m/z (fragment):
17.189 min, 41 (C2H3N+), 126 ((Et)2NCH CHC(O)+); 392
((Et)2NCH CHC(O)CF(CF3)OCF2CF(CF3)+); 558 ((Et)2
Diethylamine reacts relatively slowly with the ketones,
taking a few days to go to completion. The primary products of
these reactions are (CF3)2CFH, (CF3)2CFC(O)NHEt and
(CF3)2CF C(O)CH CHNEt2.
+
NCH CHC(O)CF(CF3)–(HFPO)2 ); 696 (M + H+ À F À
C2H5).
(CF3)2CFC(O)NHC2H5. GC/CI(Methane)/MS (70 eV,)
retention time, m/z (fragment): 4.896 min, 41 (C2H3N+) 72
(EtHNC(O)+); 222 (M À F); 242 (M + H+).
Acknowledgements
trans-(CF3)2CFC(O)CH CHNEt2. GC/CI(Methane)/MS
(70 eV,) retention time, m/z (fragment): 14.674 min, 126
(Et2NCH CHC(O)+); 276 (M + H+ À F); 296 (M + H+); 324
(M + 29).
We are grateful for the help from Paul Resnick for his gifts of
perfluoro bis-isopropyl and perfluoro ethylisopropyl ketone,
Joseph S. Thrasher from The University of Alabama and their
gift of poly(HFPO)perfluoroisopropyl ketone,. Miren Salsa-
mendi, David Yake, Fred Davidson from DuPont CCAS,
Douglas Tabor from the University of Delaware, and The
Research Staff at Jackson Laboratory, and Lori E. Stephans for
helpful discussions.
5.4.3. Reaction of poly(HFPO) methyl ester with
diethylamine
Poly(HFPO) methyl ester with diethylamine gives complete
decomposition of the methyl ester into F[CF(CF3)CF2
O]3CFHCF3.
References
5.4.4. Reaction of the poly(HFPO) perfluoroisopropyl
ketone with diethylamine
[1] A.S. Milirn, Jr., US Patent 3,214,478 (1965).
[2] J.T. Hill, J. Macromol, J. Macromol. Sci. Chem. A 8 (3) (1974)
499.
Diethylamine reacts relatively slowly with the ketones,
taking a few days to go to completion. (CF3)2CFH, was
observed along with some unexpected products: F[CF(CF3)
CF2O]3CF(CF3)C(O)NHCH2CH3 and F[CF(CF3)CF2O]3
CF(CF3)C(O)-CH CHNEt2, and F[CF(CF3)CF2O]3CFHCF3.
F[CF(CF3)CF2O]3CF(CF3)C(O)NHCH2CH3, N-ethylpo-
ly(HFPO)amide. GC/CI (Methane)/MS (70 eV,) retention
time, m/z (fragment): 9.855 min, 670 (F(HFPO)3CF(CF3)-
C(O)NHCH2CH3 + H+–HF), 690 (F(HFPO)3CF(CF3)C(O)
NHCH2-CH3 + H+).
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4285.
[4] T. Martini, US Patent 4,067,884 (1976).
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[6] W.J. Middleton, C.G. Krespan, J. Org. Chem. 30 (1965) 1398.
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[8] S.J. Falcone, US Patent 6,187,954 B1 (2001).
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281.
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