Electrophilic versus free radical reactions of halogens and halogen systems with perfluoroalkenes and a perfluoroalkylethylene

Article abstract of DOI:10.1016/S0022-1139(00)00319-5

Ionic and free radical addition of halogen systems were carried out with perfluoroheptene-1 (1), octafluorocyclopentene (2), 1H,1H,2H-perfluorooctene-1 (3) and perfluoro-4-methyl-2-pentene (4). The terminal alkene 1 was treated with chlorine in tert-butyl alcohol as solvent with mercury catalyst under reaction conditions that assure an ionic pathway. Bromine did not react with 1 under similar conditions. Chlorine monofluoride reacts with 1 in methylene chloride to give 2-chloroperfluoroheptane. Alkene 3 is more reactive and gives products with electrophiles Cl₂, Br₂, BrCl, and ICl from ring-opening of the halonium ions at the terminal carbon. Disubstituted perfluoroalkenes 2 and 4 did not react ionically with Cl₂, Br₂, BrCl, or ICl. Free radical reactions of Cl₂, Br₂, BrCl, and ICl give good yields of dihaloproducts with 1 and 3. Yields are poor for the photochemical bromination of disubstituted perfluoroalkenes 2 and 4 since the dibromoproducts are in photochemical equilibrium with the alkene.

Full text of DOI:10.1016/S0022-1139(00)00319-5

Journal of Fluorine Chemistry 106 (2000) 103±112
Electrophilic versus free radical reactions of halogens and halogen
systems with per¯uoroalkenes and a per¯uoroalkylethylene$
Dale F. Shellhamer*, Jeannette L. Allen, Rachel D. Allen, Melissa J. Bostic, Elizabeth A. Miller1,
Colleen M. O'Neill, Benjamin J. Powers, Eric A. Price, John W. Probst, Victor L. Heasley
Department of Chemistry, Point Loma Nazarene University, San Diego, CA 92106, USA
Accepted 19 June 2000
Abstract
Ionic and free radical addition of halogen systems were carried out with per¯uoroheptene-1 (1), octa¯uorocyclopentene (2), 1H,1H,2H-
per¯uorooctene-1 (3) and per¯uoro-4-methyl-2-pentene (4). The terminal alkene 1 was treated with chlorine in tert-butyl alcohol as solvent
with mercury catalyst under reaction conditions that assure an ionic pathway. Bromine did not react with 1 under similar conditions.
Chlorine mono¯uoride reacts with 1 in methylene chloride to give 2-chloroper¯uoroheptane. Alkene 3 is more reactive and gives products
with electrophiles Cl2, Br2, BrCl, and ICl from ring-opening of the halonium ions at the terminal carbon. Disubstituted per¯uoroalkenes 2
and 4 did not react ionically with Cl2, Br2, BrCl, or ICl. Free radical reactions of Cl2, Br2, BrCl, and ICl give good yields of dihaloproducts
with 1 and 3. Yields are poor for the photochemical bromination of disubstituted per¯uoroalkenes 2 and 4 since the dibromoproducts are in
photochemical equilibrium with the alkene. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Halogen systems; Per¯uoroalkenes; Polymers
1. Introduction
[21±25]. Electron-rich hydrocarbon alkenes like vinyl ethers
or vinylcyclopropanes [26] react readily with halogens by an
ionic process. Halogens are slow to react ionically with
electron-de®cient hydrocarbon alkenes and the free radical
pathway predominates. Reaction conditions to favor an ionic
process for halogenation of electron-de®cient alkenes
include absence of light, an ef®cient inhibitor, and low
concentration alkene to prevent molecule-induced homoly-
sis [21±25].
Ionic reactions with per¯uoroalkenes present an interest-
ing situation. The pi-bond is unreactive toward electrophiles
due to the electron withdrawing effect of the per¯uoroalkly
group and the vinyl ¯uorines. Knunyants and Polishuck have
shown that the C=C bond reactivity decreases toward elec-
trophilic reagents as the number of ¯uorine atoms on the
double bond increases, whereas the double bond reactivity
toward nucleophiles increases [27,28]. On the other hand,
although carbocation or radical cation per¯uorocarbon inter-
mediates are dif®cult to generate, when they are formed they
are stabilized by the lone pair of electrons on the vinyl
¯uorine as shown below [29,30]:
Radical addition of organic substrates to per¯uorocarbon
alkenes give useful synthetic intermediates [1±3], monomers
[4±8], and biocompatible materials with improved oxygen
transport capacity such as blood substitutes [8±11].2 The
presence of per¯uoroalkyl and a hydrophilic group in the
monomers increases oxygen permeability in contact lenses
[12±14] and vein-and-body-tissue prosthetics [13,14]. Ionic
reactions to per¯uoroalkenes provide another entry into
useful monomers [15±17] and even some polymers [18±
20]. Halogens are a unique reagent that can readily react via
an ionic or radical process. The ionic or radical pathway with
halogens can be favored by carefully controlling the reaction
conditions. Free radical reaction of alkenes and halogens are
initiated by light, organic initiators, or in the dark at high
concentrations of alkene by molecule-induced homolysis
$ Presented in part at the14th Winter Fluorine Conference at St.
Petersburg Beach, FL, 8 January 1999.
* Corresponding author.
E-mail address: daleshellhamer@ptloma.edu (D.F. Shellhamer).
1 Howard Hughes Scholar.
2 For example, perfluorooctyl bromide used by Alliance Pharmaceutical
Corp. as a blood substitute, liquid pulmonary oxygen carrier, and medical
imaging product can be prepared by a radical exchange of bromine with
perfluorooctyl iodide.
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 0 0 ) 0 0 3 1 9 - 5

104
D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
Ionic mechanisms have been reported for the reaction of
hydrocarbon analogs.
strong electrophiles like nitrosyl ¯uoride with per¯uorovinyl
ethers, per¯uorovinyl amines, and even tetra¯uoroethylene
when catalyzed by boron tri¯uoride [16,31,32]. The litera-
ture contains several cases where halogens are reported to
react with per¯uoroalkenes by an ionic pathway [33,34].
The lack of solvent incorporation in many of these reactions
with protic solvents made us suspicious of these claims. Our
experience is that, in order to eliminate free radical initiation
by molecule-induced homolysis, halogen and interhalogen
reactions of alkenes with electron-de®cient pi-bonds must
be carried out in the dark with free radical inhibitors and at
low concentration of alkenes [24]. We suspect that many of
the halogen reactions with per¯uoroalkenes, represented as
ionic reactions in the literature, are in reality free radical
reactions, or that at least have a competing free radical
pathway.
Our goal in this paper is to study the free radical and ionic
reactions of some halogens and halogen systems with mono-
and disubstituted per¯uoroalkenes 1 and 2, and with the
per¯uoroalkylethylene 3. We will demonstrate the reaction
conditions, if they exist, that are necessary to force these
unreactive alkenes to proceed via an ionic pathway. The
regiochemistry of products from terminal alkenes 1 and 3
will be compared to ionic and free radical reactions of their
2. Results
Products from photochemical reactions of 1, 2, 3, and
per¯uoro-4-methyl-2-pentene (4) with halogens, interhalo-
gens and tert-butylhypochlorite are listed in Table 1. 1-
Alkoxy-2-haloproducts isolated from the ionic reactions are
given in Table 2. Regioisomers for reaction of 1 with BrCl,
ICl or t-BuOCl were determined by 19F NMR and mass
spectrometry. The chemical shift for the terminal ¯uorines
(±CF2X) was at 74.0 ppm for X ˆ OtBu with Cl on
carbon-2. With chlorine, bromine or iodine on carbon-2,
the chemical shift on carbon-1 for ±CF2X was between 60
and 68 ppm for X ˆ Cl; between 57 and 59 ppm for
X ˆ Br; at 53.1 for X ˆ I. Mass spectral fragments for
‡
‡
[CF2-I] and isotope clusters for [CF2-X] (X ˆ Cl or Br)
are also consistent with the assigned structures. Ionic reac-
tion of ClF with 1 gave only the 2-chloroisomer. Con®rma-
Table 1
Photochemical reactions of halogens and halogen systems with perfluoroheptene-1 (1), 1H,1H,2H-perfluoro-1-octene (3), octafluorocyclopentene (2), and
perfluoro-4-methyl-2-pentene (4)
Alkene
Halogen system
Conditionsa
Yield
Product distribution
Mb
Dihalo
aMb
1
1
1
1
1
3
3
3
3
2
2
2
4
Cl2
258, 3 daysc
258, 15 h
08, 40 min
08, 3 h
91c,d
67d
55e
15d
62d
95d
99d,h
97i
±
±
100
100
±
±
Br2
BrCl
ICl
20
33
±
63f
17
52
100
±
15g
tBuOCl
Cl2
08, 1 h
±
258, 15 min
1208, 5 h
08, 20 min
08, 3 h
08, 30 min
258, 2 h
±
100
Br2
±
100
39j
6g
73/27k
92/8k
(65/20)l
100
±
BrCl
ICl
18
2
43
92
±
87d
92d
ꢀ3
Cl2
±
Br2
±
±
BrCl
Cl2
08, 5 h
08, 12 h
60e
71d
±
±
±
±
a Sunlamp 300 W.
b Markovnikov products are the 1-bromo-2-chloroisomer or the 2-chloro-1-iodoisomer; aM: anti-Markovnikov.
c See [67].
d Isolated yields.
e Yield by gas chromatography with perfluorooctyl bromide as internal standard corrected for flame response.
f Percent 1,2-dibromo- to 1,2-dichloroperfluoroheptane (48:15).
g 1,2-dichloroproduct. No 1,2-diiodoproduct detected.
h See [54].
i Yield by NMR with toluene as internal standard.
j Percent 1,2-dibromo- to 1,2-dichloroproduct (11:28).
k Product distribution trans/cis.
l Products 1-Bromo-2-chloroperfluorocyclopentane trans/cis (65/20), 1,2-dichloroperfluorocyclopentane trans/cis (11/4). No 1,2-dibromoproducts were
detected.

D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
105
Table 2
Ionic reactions of halogens and interhalogens with perfluoroheptene-1 (1) and 1H,1H,2H-perfluoro-1-octene (3)
Alkene
Electrophile Catalyst
Solvent
Percent products formed
(reaction time)
Product distributiona
M
Dihalo
aM
1-Alkoxy-2-
haloproduct aMb
1
1
3
3
3
3
3
3
3
3
3
Cl2
ClF
Cl2
Cl2
Br2
Br2
BrCl
BrCl
ICl
Hg(OAc)2
tBuOH
10c (2 weeks)
20c (2 h)
±
±
±
±
±
±
4
±
±
±
±
96
±
±
100
±
4.0
±
±
CH2Cl2
CH3NO2
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
CH3OH
±
<1c (6 h)
100
28
87
9
25e
18f
±
±
HgSO4
±
5c (72 h)
±
72
20d (9 days)
5c (5 days)
20d (4 days)
20d (4 days)
10c (5 days)
20c (5 days)
80d (18 h)
±
13
91
HgSO4
±
±
60
47
5
11
HgSO4
±
HgSO4
35
95
ICl
±
<1
±
>99
100
g
ICl
AgNO3
±
a Markavnikov products are the 1-bromo-2-chloroisomer or the 2-chloro-1-iodoisomer.
b No Markovnikov 2-alkoxy-1-haloproducts detected.
c Yield by gas chromatograph with perfluorooctyl bromide as internal standard corrected for flame response.
d Yield by NMR with toluene as internal standard.
e Percent 1,2-dibromo- to 1,2-dichloroproduct (10:15).
f 1,2-Dibromo product. No 1,2-dichloroprdocut detected.
g One equivalent of AgNO3 added.
tion of its structure was established by comparison of the 19
F
the dibromo products are in equilibrium with 2 under
ultraviolet illumination which explains the low yield. Low
conversion was also found for the photochemical reaction of
ICl with 2 due to equilibration. Yields were good for the
photochemical reaction of chlorine with the acyclic alkene
per¯uoro-4-methyl-2-pentene (4). Photochemical bromina-
tion of 4 also resulted in a low conversion. Products from the
bromination of 4 and reaction of ICl with 2 were not isolated
due to the low conversion of these disubstituted alkenes.
NMR and MS to an authentic sample from professor
Lagow's laboratory at the University of Texas at Austin
(see Acknowledgements).
Regioisomers from reaction of halogen systems with the
per¯uoroalkylethylene 3 were readily assigned from 13C
NMR data of carbons 1 and 2. Carbon-1 was a broad singlet
while carbon-2 was found to be a triplet with C±F coupling
of 22±25 Hz. The 13C chemical shifts of carbons 1 and 2 for
products from halogen systems and alkene 3 are character-
istic. For example, the chemical shift of carbon-2
(C6F13CHX±CH2Y) ranged from 55.0 to 57.3 ppm for
X ˆ Cl; 44.8 to 46.5 ppm for X ˆ Br and 22.2 to
23.5 ppm for X ˆ I. Con®rmation of the structure
3,3,4,4,5,5,6,6,7,7,8,8,8-trideca¯uoro-2-iodo-1-methoxyoc-
tane was made by reduction of the iodine with tributyltin
3. Discussion
3.1. Ionic reactions
Reactions were carried out in the dark, very dilute alkene
(0.02 mol fraction or less), and under oxygen to ensure an
ionic pathway. Oxygen is an effective radical scavenger of
chlorine atoms but is less effective as a scavenger for
bromine or iodine atoms in the chain-transfer steps [24].
Control experiments with isoamyl nitrite did not alter the
slow rate of these reactions in aprotic solvents. Solvent
incorporation with methanol and tert-butanol con®rmed
an ionic reaction in protic solvents.
A mercury (II) catalyst was required to force per¯uor-
oheptene-1 (1) to give a slow ionic reaction in protic solvent
(Table 2). We believe this is the ®rst con®rmed ionic
chlorination of alkene 1. Bromine monochloride did not
react with 1 in methanol under similar reaction conditions.
In methylene chloride as solvent, Cl2, BrCl, or ICl did not
react ionically with 1. Thus, a more reactive electrophile
than Cl2 is required to react ionically with a terminal
‡
1
hydride. Mass spectral fragments [±CH2X] and H NMR
data were also consistent for the regioisomers obtained from
reactions with alkene 3.
Products from octa¯uorocyclopentene (2) were isolated
and characterized as a mixture of trans- and cis-isomers.
Mass spectral and infrared data are on separate isomers as
they were resolved by GC-MS and GC-FTIR. It was
assumed that the cis-isomer had the longer retention time
as it was the minor isomer. The relative amount of cis-isomer
decreases for the series Cl2 > BrCl > Br2 (Table 1). This
trend in the trans/cis ratio re¯ects the steric effect in the
chain propagation step [35±37]. Isolated yields are good for
the dichloro- and bromochloroocta¯uorocyclopentanes.
However, the yield was <5% for the photochemical bromi-
nation of 2. Dibromoocta¯uorocyclopentanes were obtained
by combining several runs. Control experiments show that

106
D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
per¯uoroalkene like 1 in an aprotic solvent. We recently
showed that halogen mono¯uorides (XF) generated from X2
(X ˆ Cl, Br, or I) and ¯uorine gas or XF3 are a very reactive
species compared to XF from N-halosuccinimides and
amine hydrogen ¯uorides [38,39]. Reaction of dilute 1
and molecular ClF, in the dark, without catalyst, in an
aprotic solvent gave a slow ionic reaction (Table 2). The
data in Table 2 show that the chloronium ion from alkene 1 is
opened at the terminus to give only the anti-Markovnikov
(aM) regioisomer. In the literature reactive halogen mono-
¯uorides (XF; X ˆ Cl, Br, or I) with terminal per¯uoroalk-
enes give only the 2-haloper¯uoro products even though
some of these reactions were carried out neat [40±43].
Apparently, these interhalogen mono¯uorides are suf®-
ciently electrophilic so that they do not undergo a mole-
cule-induced homolysis even with electron-de®cient
terminal per¯uoroalkenes. Chlorine mono¯uoride generated
from N-chlorosuccinimide and triethylamine trihydrogen-
¯uoride produces a sluggish electrophile [38] and it did not
react with alkene 1.
The halogen electrophiles Cl2, Br2, and ICl are more
reactive with alkene 3 than per¯uoroalkene 1 (Table 2).
There is even a slow reaction of Cl2 with 3 in nitromethane
without catalyst. Ring opening of the halonium ion from 3
by methanol is only at the terminal carbon (aM isomer).
Bromonium ions from terminal per¯uoroalkylethylenes
with mercuric acetate in acetic acid are also opened at
the terminal carbon [44]. The uncatalyzed reaction of BrCl
in methanol with 3 gives a small amount of Markovnikov
(M) product. This is in contrast to opening of the halonium
ion in terminal hydrocarbon alkenes where the Markovnikov
product is generally the major isomer in aprotic or protic
solvent [38,39,45±49].3 Haufe has shown that electron-with-
drawing groups in the allylic position of a hydrocarbon
terminal alkene increases the amount of anti-Markovnikov
products for bromo¯uorination [50]. The strong in¯uence of
a per¯uoroalkyl group on the halonium ions from 3 desta-
bilizes the positive charge located on carbon-2. Therefore,
we suggest that the halonium ion from 1-hexene is rather
symmetrical [45], and that the halonium ions from 1 and 3
are slightly unsymmetrical as shown below:
formed. An unsymmetrical and open ion were reported
for the ionic bromination of 1-hexyne [45] and phenylace-
tylene [52], respectively, as shown below:
The disubstituted per¯uoroalkenes 2 and 4 could not be
forced to react with chlorine by an ionic pathway even with
metal catalysts in protic solvents. These results are due to the
strong electron-withdrawing and large steric effect encoun-
tered by two per¯uoroalky groups on a per¯uoroalkene [17].
Similar results were found for a series of disubstituted
per¯uoroethylenes [53±56].4
3.2. Free radical reactions
Free radical additions to terminal hydrocarbons [26,57±
59], per¯uoroalkylethylenes [60,61] and per¯uoroalkenes
[62] occur mainly on the terminal carbon. Our data from
tert-butylhypochlorite and alkene 1 also support these obser-
vations (Table 1). The radical prefers to be on the number 2
carbon even though a per¯uoroalkyl group is inductively
destabilizing [59]. A radical on carbon-1 would not be
stabilized from the donating resonance of both ¯uorines
since per¯uorocarbon radicals are pyramidal [59]. The over-
all effect of the two terminal ¯uorines is to inductively
destabilize a radical on the terminal carbon [59]. However,
free radical addition of ICl to 1 gives both Markovnikov and
anti-Markovnikov products (Table 1). A recent paper on the
free radical reactions of ICl with 1,1-di¯uoroethylene
reports that ClCF2CH2I is the major regioisomer [63±66].
Their experimental data and semi-empirical calculations
indicate that the iodine atom prefers to add so that the
radical is on the carbon with both ¯uorines [63]. This
unusual regiochemistry was also observed for radical addi-
tion to several 1,1-di¯uoroalkenes [63±66].5
Radicals from alcohols and cyclic ethers add to the
terminal carbon of per¯uoroalkylethlyene 3 [61]. Destabi-
lization by the per¯uoroalkyl group in 3 is not suf®cient to
cause radicals from alcohols and cyclic ethers to alter the
regiochemistry by adding to carbon-2 and placing the radical
on carbon-1 [61]. However, free radical reaction of BrCl or
ICl with 1 and 3 give signi®cant amounts of Markovnikov
products (Table 1). Since bromine chloride is in equilibrium
with Cl2 and Br2, product distributions from photochemical
reaction of BrCl with alkenes 1, 2, and 3 may not give useful
mechanistic data because the alknene or haloper¯uoroalkyl
radical may interact with Cl2 or Br2 in the chain-transfer or
propagation steps. Photochemical equilibration of ICl may
also occur.
This is in contrast to the halonium ions from vinylcyclo-
propanes [26] and cyclopropyl acetylene [51] where non-
bridged, non-classical cyclopropylcarbinyl cations are
3 Reaction of ICl with 1-hexene in methanol gives ca. 50% solvent
incorporated products where the M 1-iodo-2-methoxyhexane favors the
aM 2-iodo-1-methoxyhexane by 5:1.
4 Reaction of halogens in sulfur trioxide/water is a rare example, see
[55,56].
5 Other examples include [64±66].

D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
107
4. Experimental
4.2.3. Reaction of tert-butyl hypochlorite with 1
A neat mixture of 350 mg (1.00 mmol) 1 and 88 mg
(0.83 mmol) t-butyl hypochlorite at 08 with stirring was
illuminated for 1 h with the sunlamp. Distillation 88±908 at
55±57 Torr gave 235 mg (62% yield) of 1-tbutoxy-2-chlor-
oper¯uoroheptane which was >94% pure by GC analysis. 1H
NMR (300 MHz, CDCl3)d ˆ 1:49 (s). 19FNMR (282 MHz,
CDCl3) d ˆ 74:0 (AB pattern, 2F), 81.2 (t, J ˆ 10:7 Hz,
4.1. General procedures and instrumentation
High-®eld NMR spectra were recorded on a Varian
Gemini 300 (University of San Diego). Spectra are refer-
enced relative to (CH3)4 Si or CFCl3 (d ˆ 0 ppm). GC-MS
data were recorded on a Hewlett-Packard 5970B Mass
Selective Detector (70 eV) interfaced to a HP5890 gas
chromatograph. Gas chromatography analysis was accom-
plished on an HP5890 (FID detector). The GC and GC-MS
analyses were done with a 25 m HP ultraperformance
column of internal diameter 0.20 mm with methyl silicone
as the stationary phase of 0.33 mm ®lm thickness. Initial
temperature 358C for 2 min, then ramp 58C/min to 2008C.
Infrared spectra were recorded neat (KBr plates) with a
Nicolet 620 FT spectrometer. Gas-phase infrared were
obtained on the Nicolet 620 interfaced with an HP 5890
gas chromatograph. The 25 m column for GC-FTIR
analysis was identical to that used for GC and GC-MS
analyses except for the internal diameter of the column
which was 0.30 mm. Exact masses were obtained at the
University of California, Riverside. Errors in exact masses
are <4 ppm. Preparative GC was carried out with a
Hewlett-Packard F&M GC (t.c. detector) on a 1/4
in: Â 10 ft stainless steel column of 20% OV-210 on
80/100 Chromosorb W-H.P.
3F), 115.3 (m, 2F), 120.0 (m, 2F), 122.8 (m, 2F),
1
126.4 (m, 2F), 136.1 (m, 1F). IR (neat KBr, cm
2991(m), 2940(w), 1305(m), 1243(s), 1145(s), 1021(w),
)
‡
959(m), and 736(m). GC-MS (m/e, rel. intensity) M -15
445 and 443 (31 and 100), 219 (14), 169 (13), 148 (8), 131
‡
(21), 119 (12), 69 (59), 57 (97). HRMS (EI) calcd. for M -
15 442.9884; found 442.9893.
4.2.4. Reaction of Iodine monochloride with 1
A stirred mixture at 08 of 425 mg (1.21 mmol) 1 and
1.45 g (8.95 mmol) iodine monochloride was irridated with
the sunlamp for 3 h. The liquid at 08 was decanted from the
solid. Analysis by GC showed 1,2-dicholorper¯uorohep-
tane, 2-chloro-1-iodoper¯uoroheptane and 1-chloro-2-iodo-
per¯uoroheptane and to be formed in a ratio of 1.0:2.2:3.5,
respectively. Bulb±bulb distillation 63±688at 50 Torr gave
62 mg (10% yield) of both regioisomers in 99% purity by
GC analysis. The mixture of distilled isomers was barely
resolved on the GC-MS, but not on the GC-FTIR column.
Data below, except MS, are on the distilled mixture. Regioi-
somers are assigned on the basis of their MS fragments
4.2. Photochemical reactions
‡
[CF2-X] ; which are also consistent with the 19F chemical
shifts for ±CF2X. 19F NMR (282 MHz, CDCl3) d ˆ 53:1
(AB pattern, 2F, CF2I), 60.5 (AB pattern, 2F, CF2Cl),
81.3 (t, J ˆ 10 Hz, 6F), 105.1 (AB pattern, 2F), 114.1
(m, 2F), 119.2 (m, 2F), 119.8 (AB pattern, 2F), 122.8
(AB pattern, 2F), 123.1 (m, 2F), 124.3 (m, 1F), 126.5
(AB pattern, 2F), 126.6 (m, 2F), 137.4 (m, 1F). GC-
FTIR (gas, cm 1) 1351(w), 1242(s), 1213(m), 1152(m),
1037 (w), 981 (w), 875 (w), and 728 (w). GC-MS (m/e,
rel. intensity). 2-Chloro-1-iodoper¯uoroheptane (retention
Photochemical reactions were accomplished with a
300 W sunlamp.
4.2.1. Reaction of chlorine with perfluoroalkene-1 (1)
Chlorine gas was bubbled into neat 1 at 08 until all of
the alkene reacted as determined by GC analysis. Our 19F
NMR, IR and MS data were identical to that reported in
[67].
‡
‡
time 8.8 min) M 514 and 512 (0.2 and 0.5), M -Cl 477
‡
4.2.2. Reaction of bromine with 1
(0.3), M ±I 387 and 385 (10 and 29), 331 (6), 299 and 297 (4
‡
To 1.36 g (3.88 mmol) alkene 1 was added 640 mg
(4.00 mmol) bromine. The mixture was stirred without
cooling and with illumination by the sunlamp for 15 h.
Short path distillation 74±768 at 44 Torr gave 1.33 g
(67% yield) of 1,2-dibromoper¯uoroheptane which was
>95% pure by GC analysis. 19F NMR (282 MHz, CDCl3)
d ˆ 57:3 (m, 2F, CF2Br), 81.4 (t, J ˆ 10 Hz, 3F, CF3),
111.2 (AB pattern, 2F), 119.3 (AB pattern, 2F), 122.9
(m, 2F), 126.5 (m, 2F), and 131.2 (m, 1F, CFBr). GC-
FTIR (gas, cm 1) 1352(w), 1242(s), 1213(s), 1151(m),
1041(w), 974(w), 912(w), 871(w), and 716(w). GC-MS
and 12), 227 (5), 219 (13), [CF2I] 177 (15), 169 (12), 149
and 147 (9 and 28), 131 (39), 127 (19), 119 (21), 69 (100). 1-
‡
Chloro-2-iodoper¯uoroheptane (retention time 9.1 min) M
‡
514 and 512 (7 and 23), M -Cl 477 (7), 331 (13), 299 and
297 (3 and 8), 239 (9), 219 (16), 169 (13), 149 and 147 (8 and
27), 131 (65), 127 (29), [CF2Cl] 87 and 85 (5 and 16), 69
(100). HRMS (EI) calcd. for C7F14ClI 511.8509; found
511.8501.
‡
4.2.5. Reaction of bromine chloride with 1
A stirred solution at 08 of 350 mg (1.00 mmol) 1 and
1.30 ml of 0.95 M BrCl in methylene chloride6 was irra-
diated with the sunlamp for 40 m. Analysis by GC showed
the 1,2-dichloroper¯uoroheptane, 1-bromo-2-chloroper-
¯uoroheptane, 2-bromo-1-chloroper¯uoroheptane, and
‡
(m/e, rel. intensity) 431 and 429 (M -Br, 32), 343 and
341 (6), 219 (14), 193 and 191 (14), 181 and 179 (10),
169 (15), 131 (71), 129 (25), 69 (100). HRMS (EI) for
C7F14Br2 calcd. 507.8143; found 507.8153.

108
D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
1,2-dibromoper¯uoroheptane to be formed in a ratio of
1.0:1.3:1.1:3.1, respectively. The yield by GC with 1-bro-
moper¯uorooctane as internal standard was 55%. The chlor-
obromo-regioisomers were isolated as a mixture by
preparative GC and found by GC-FID analysis on the
capillary column to be >98% pure. Data below are on the
mixture except for the GC-MS data where the regioisomers
were barely resolved. Regiochemistry was assigned on the
reacted. GC analysis showed a trans±cis ratio of 11:1.
Several reactions were combined and the 1,2-dibromoper-
¯uorocyclopentanes were distilled, bp 50±538 at 147 Torr,
and found to be >98% pure by GC analysis. 19F NMR
(282 MHz, CDCl3), d ˆ 106:7(m, 1F), 107.6 (m, 1F),
122.6 (m, 2F), 125.5 (m, 2F), 127.6 (m, 1F), 128.5
(m, 1F). GC-MS (m/e, rel. intensity) trans, retention time
‡
‡
5.3 min M 374, 372, and 370 (0.6, 1.1, and 0.8), M -Br 293
‡
‡
basis of their MS fragments [CF2X] which are also con-
and 291 (100 and 91), M -C2F5 255, 253, and 251 (3, 4, and
2), 243 and 241 (6 and 5) 193 and 191 (50 and 43), 162 (14),
160 (9), 143 (9), 131 (19), 124 (4), 112 (10), 100 (9), 93 (26),
sistent with the 19F chemical shifts for ±CF2X. 19F NMR
(282 MHz, CDCl3) d ˆ 59:0 (AB pattern, 2F, CF2Br),
62.3 (m, 2F, CF2Cl), 81.3 (t, J ˆ 10 Hz, 6F), 111.6
(AB pattern, 2F), 114.5 (m, 2F), 117.8±121.6 (m, 4F),
122.9 (m, 4F), 126.5 (m, 4F), 128.9 (m, 1F), 133.9
(m, 1F). GC-FTIR (gas, cm 1) 1346 (w), 1246(s), 1212(m),
1145(w), 1041(w), 990(w), and 731(w). GC-MS (m/e, rel.
intensity) 1-Bromo-2-chloroper¯uoroheptane (retention
‡
81 and 79 (3 and 3), 69 (19) cis, retention time 5.7 min M
‡
374, 372, and 370 (41, 64, and 35), M -Br 293 and 291 (24
‡
and 18), M -C2F5 255, 253 and 251 (5,6, and 6), 243 and
241 (6 and 6), 193 and 191 (100 and 60), 162 (18), 160 (11),
143 (14), 131 (27), 124 (13), 112 (15), 100 (14), 93 (48), 84
(17), 81 and 79 (5 and 4), 69 (25). HRMS (EI) calcd. for
C5F8Br2 369.8239; found 369.8240.
‡
time 5.3 min) M -Br 387 and 385 (1.5 and 4.6), 299 and
297 (4 and 12), 219 (22), 197 (12), 169 (15), 149 and 147 (7
and 21), 131 and 129 (62 and 28), 119 (20), 87 and 85 (5 and
14), 69 (100). 2-Bromo-1-chloroper¯uoroheptane (retention
4.2.8. Reaction of bromine chloride with 2
The reaction was carried out as described for the photo-
chemical reaction of BrCl with 1. Analysis by GC showed
the reaction to be complete in 5 h and the yield to be 60%
with 1-bromoper¯uorooctane as internal standard. The ratio
of products was trans-1,2-dichloroper¯uorocyclopentane,
cis-1,2,-dichloroper¯uorocyclopentane, trans-1-bromo-2-
‡
time 5.4 min) M -Cl 431 and 429 (0.6 and 0.5), 362 and 360
(6 and 6), 343 and 341 (1 and 1), 197 and 195 (10 and 8), 193
and 191 (8 and 8), 169 (5), 131 (24), 119 (10), 87 and 85 (32
‡
and 100), 69 (53). HRMS (CI, MH -HF) calcd. for
C7F13BrCl 444.8664; found 444.8670.
chloroper¯uorocyclopentane,
cis-1-bromo-2-chloroper-
4.2.6. Reaction of chlorine with octafluorocyclopentene 2
3.43 g (16.2 mol) Alkene 2 and a 1.5 mole excess chlorine
in a 1 liter vessel, without cooling, was illuminated with the
sunlamp for 30 m. Short path distillation, bp 41±428 at
139 Torr (lit. 84±858 at 760 Torr) [68,69]7 gave 4.21 g
1,2-dichloroper¯uorocyclopentane which was 99% pure
by GC analysis. The trans and cis isomers are just resolved
on the capillary column with a retention time of 2.2 and
2.3 m, respectively. The major isomer, 2.2 min, was
assigned the trans structure and their ratio by GC analysis
was 2.7:1.0. Spectral data not given in the literature follow.
19F NMR (282 MHz, CDCl3) is on the mixture.
d ˆ 112:3(m, 1F), 113.2 (m, 1F), 123.8 (m,1F),
127.0 (m, 2F), 130.2 (m, 1F), 131.1 (m,1F). GC-MS
(rel. intensity) trans (2.2 min) M‡35-Cl only 282 (0.4), 167,
165, and 163 (0.6, 9, and 14), 149 (60), 147 (100), 131 (45),
116 (29),109 (13), 100 (43), 93 (41), 87 and 85 (4 and 14), 74
(14), 69 (70), 50 (13), 31 (65) cis (2.3 min) M‡ 35Cl only 282
(0.1), 167, 165, and 163 (0.5, 7, and 10), 149 (47), 147 (100),
131 (23), 116 (20), 109 (8), 100 (24), 93 (29), 87 and 85 (3
and 10), 74 (8), 69 (41), 50 (6), 31 (35).
¯uorocyclopentane, 3.4:1.0:19.9:6.2, respectively. The
trans- and cis-bromochloro isomers were collected as a
mixture by preparative GC and they were resolved by
NMR and GC-MS. 19F NMR (282 MHz CDCl3) trans-1-
bromo-2-chloroper¯uorocyclopentane d ˆ 107:6 (dm,
J ˆ 250 Hz, 1F), 111.8 (dm, J ˆ 246 Hz, 1F), 122.9
(m, 3F), 128.7 (dd, J ˆ 169:0 and 12.8Hz, 1F), 129.2 (m,
1F), 129.6 (dd, J ˆ 196:7 and 12.8 Hz, 1F) cis-1-Bromo-
2-chloroper¯uorocylopentane
d ˆ 107:7
(dm,
J ˆ 245 Hz, 1F), 114.1 (dm, J ˆ 246 Hz, 1F), 119.7
(dm, J ˆ 250 Hz, 1F), 123.0 (dm, J ˆ 240 Hz, 1F),
124.3 (dm, J ˆ 250 Hz, 1F), 127.4 (dm, J ˆ 250 Hz,
1F), 135.6 (m, 1F), 139.3 (m, 1F). GC-MS (rel. intensity)
‡
trans, retention time 3.5 min M 330, 328, and 326 (0.7, 2.9,
‡
and 2.2), M -Br 249 and 247 (7 and 23), 193 and 191 (35
and 36), 149 and 147 (31 and 100), 131 (45), 100 (37), 93
‡
(56), 69 (71) cis, retention time 3.7 min M 330, 328 and
326 (2.7, 10.8, and 8.9), 249 and 247 (1 and 4), 193 and 191
(42 and 41), 149 and 147 (32 and 100), 131 (34), 100 (26), 93
(50), 69 (47). HRMS (EI) calcd. for C5H8BrCl 325.8744;
found 325.8733.
4.2.7. Reaction of bromine with 2
4.2.9. Reaction of chlorine with 1H,1H,2H-perfluoro-1-
octene 3
To a 10 ml round bottom ¯ask with a Te¯on-coated
stirring bar, was added 1.0 ml carbon tetrachloride, 78 mg
(0.37 mmol) alkene 2 and 56 mg (0.35 mmol) bromine. The
glass stopper was wired to the ¯ask and its contents illu-
minated with the sunlamp without cooling. After 2 h the
reaction seemed to reach equilibrium and <5% of 2 had
Chlorine gas was bubbled into 3.42 g (0.010 mol) alkene
3 at room temperature with stirring and illumination by the
sunlamp for 15 m. Distillation bp 85±868 at 45 Torr gave
3.96 g (95% yield) of 1,2-dichloro-1H,1H,2H-per¯uorooc-
tane which was 98% pure by GC analysis. 1H NMR

D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
109
(300 MHz, CDCl3). d ˆ 3:76 (dd, J ˆ 11.7 and 8.8 Hz, 1H),
4.09 (dd, J ˆ 11:7 and 2.9 Hz, 1H), 4.48 (tdd, J ˆ 11:6, 8.8,
and 2.9 Hz 1H). 13C NMR 75.4 MHz, CDCl3) d ˆ 42:4 (brd.
s), 57.0 (t, J ˆ 25 Hz). 19F (282 MHz, CDCl3) d ˆ 81:4 (t,
J ˆ 10 Hz, 3F), 116.9 (AB pattern, 2F), 120.2 (AB
pattern, 2F), 122.3 (AB pattern, 2F), 123.2 (m, 2F),
126.6 (AB pattern, 2F). GC-FTIR (gas, cm 1). 2985(w),
1443(w), 1345 (w), 1243 (s), 1149(m), 844(w), 809(w),
standard was 97%. Short path distillation at 20 Torr gave,
fraction-1 0.757 g boiling range 69±768, and fraction-2
1.485 g boiling range 76±808. The bromochloride regioi-
somers were separated from the dichloro- and dibromopro-
ducts by preparative GC and were a ratio of 1.0:2.4 with the
2-bromo-1-chloroproduct as the major regioisomer. Spectral
data are on the mixture of regioisomers and they are
completely resolved by 13C NMR and GC-MS. 2-Bromo-
1-chloro 1H,1H,2H-per¯uorooctane. 13C NMR (75.4 MHz,
CDCl3) d ˆ 42:9 (brd. s), 46.5 (t, J ˆ 25 Hz). GC-MS (rel.
‡
738(w), 708(w). GC-MS (rel. intensity) M 420, 418, and
‡
416 (0.06, 0.3, and 0.5), M -Cl 383 and 381 (0.08 and 0.3),
‡
149 (13), 147 (22), 131 (25), 119 (17), 111 (26), 100 (22), 99
(65), 97 (100), 87 and 85 (8 and 32), 83 (27), 77 (25), 69
(92), 67 (29), 61 (30), 51 (45), 49 (70). HRMS (EI) calcd. for
C8H3F13Cl2 415.94042; found 415.94040.
intensity) retention time 11.8 m M 464, 462, and 460 (4,
‡
‡
21, and 15), M -Cl 427 and 425 (1.0 and 1.0), M -Br 383
and 381 (27 and 80), 363 and 362 (0.5 and 1.4), 311(11), 145
and 143 (10 and 37), 141 (25), 131, 129, and 127 (31, 30, and
20), 119(19), 113(29), 111(69), 100 (16), 95 (8), 93 (11), 77
(46), 69 (100), 67 (43), 51 (50), 49 (47). 1-Bromo-2-chloro-
1H,1H,2H-per¯uorooctane. 13C NMR (75.4 MHz, CDCl3)
d ˆ 42:5 (brd. s), 57.3 (t, J ˆ 25 Hz). GC-MS (rel. inten-
4.2.10. Reaction of iodine monochloride with 3
Reaction of 5.19 g (0.015 mol) 3 was carried as described
above for the photochemical reaction of ICl with 1 and it was
complete in 3 h. Analysis by GC showed 1,2-dichloro-
‡
sity) retention time 11.7 m M -Br 383 and 381 (34 and 100),
1H,1H,2H-per¯uorooctane,
1-chloro-2-iodo-1H,1H,2H-
311 (9), 145 and 143 (5 and 20), 131, 129, and 127 (14, 11,
10), 119 (15), 113 (7), 111 (11), 100 (10), 95 (15), 93 (16),
77 (21), 69 (55), 67 (33), 51 (26), 49 (16). HRMS (EI) calcd.
for the regioisomers C8H3F13BrCl 459.8899; found
459.8908. The following data are from partially resolved
regioisomers. 2-Bromo-1-chlororegioisomer 1H NMR
(300 MHz, CDCl3) d ˆ 3:82 (dd, J ˆ 12:5 and 7.8 Hz,
1H), 4.15 (dd, J ˆ 12:5 and 3.7 Hz, 1H), 4.49 (tdd,
J ˆ 16:5, 7.8 and 3.7 Hz, 1H due to minor regioisomer).
19F NMR (282 MHz, CDCl3)-81.4 (t, J ˆ 10 Hz, >3F due to
minor isomer), 111.8 (AB pattern, 2F), 119.5 (AB
pattern, 2F), 122.2 (m, 2F), 123.1 (m, 2F), 126.6
(m, 2F). The regioisomers did not resolve on the GC-FTIR
(gas, cm 1) 2981(w), 1443(w), 1345(w), 1243(s), 1148(m),
1059(w), 842(w), 809(w), 713(w).
per¯uorooctane and 2-chloro-1-iodo-1H,1H,2H-per¯uor-
ooctane to be formed in a ratio of 1.0:46:3.0, respectively.
Distillation bp 70±718at 6.0 Torr gave 6.72 g (87% yield) of
the chloro-iodo products which was 98% pure with one
fraction that was >99% the 1-chloro-2-iodo regioisomer. 1H
NMR (300 MHz, CDCl3) d ˆ 3:82 (dd, J ˆ 12:8 and
8.4 Hz, 1H), 4.03 (dd, J ˆ 12:8 and 4.2 Hz, 1H), 4.62
(tdd, J ˆ 13:1, 8.4 and 4.2 Hz, 1H). 13C (75.4 MHz, CDCl3)
d ˆ 23:5 (t, J ˆ 24 Hz), 44.5 (brd. s). 19F NMR (282 MHz,
CDCl3) d ˆ 81:4 (t, J ˆ 9 Hz, 3F),
98.2 (dm,
J ˆ 275 Hz, 1F), 110.9 (dm, J ˆ 275 Hz, 1F), 118.9
(AB pattern, 2F), 122.2 (m, 2F), 123.1 (m, 2F), 126.6
(m, 2F). GC-FTIR (gas, cm 1) 2978(w), 1445(w), 1344(w),
1243(s), 1149(m), 1051(w), 841(w), 809(w), 711(m). GC-
‡
MS (rel. intensity) retention time 15.0 m. M 510 and 508
‡
(15 and 46), M -I 383 and 381 (18 and 54), 313 (10), 311
4.2.12. Reaction of chlorine with perfluoro-4-methyl-2-
pentene 4
(20), 141 (8), 131 (16), 127 (28), 119 (22), 11 (16), 77 (56),
69 (100), 67 (75), 51 (45), 49 (29). HRMS (EI) calcd. for
C8H3F13ClI 507.8760; found 507.8746. Data for 2-chloro-1-
iodo-1H,1H,2H-per¯uorooctane (minor isomer) from
resolved GCFT-IR and GC-MS of the crude reaction mix-
ture. GCFT-IR (gas, cm 1) 2950(w), 1352(w), 1243(s),
1149(m), 1057(w), 850(w), 809(w), 736(m). GC-MS (rel.
Chlorine of 0.71 g (0.010 mol) was condensed at 788 in
a 25 ml round bottom ¯ask with 2.67 g (0.0092 mol) alkene
4 and a Te¯on-coated magnetic stirring bar. The stopper was
wired to the ¯ask and the stirred mixture irridated for 12 h
without cooling. Distillation, bp 60±628at 133 Torr gave
1.96 g (71% yield) 2,3-dichloro-4-methylper¯uoropentane
which was found to be 99% pure by GC analysis. The
erythro threo isomers are formed in ca. equal amounts
and their identity undetermined 19F NMR (282 MHz CDCl3)
d ˆ 68:9 (m, 3F), 69.3 (m, 3F), 69.8 (m, 6F), 74.2
(m, 3F), 74.6 (m, 3F), 123.5 (m, 1F), 125.2 (m, 1F),
130.3 (m, 2F), 169.9 (m, 1F), 170.3 (m, 1F). Stereo-
isomers not resolved on GC-FTIR (gas, cm 1) 1255(s),
1155(m), 1104(w), 979(w), 865(w), 731(w), 689(w). GC-
‡
intensity) retention time 14.7 min M 510 and 508 (3 and 9),
‡
M -I 383 and 381 (34 and 92), 313 (7), 311 (17), 141 (17),
131 (16), 127 (19), 119 (23), 111 (9), 77 (77), 69 (100), 67
(54), 51 (54), 49 (27).
4.2.11. Reaction of bromine monochloride with 3
The reaction was carried out as described above for the
photochemical reaction of BrCl with 1 on 3.46 g (0.010 mol)
alkene 3 and was complete in 20 m. Analysis by GC showed
the ratio of products to be dichloroproduct, 1-bromo-2-
chloro-1H,1H,2H-per¯uorooctane, 2-bromo-1-chloro-1H,
1H,2H-per¯uorooctane, dibromoproduct 2.5:1.6:3.9:1.0,
respectively. The yield by 1H NMR with toluene as internal
‡
MS (rel. intensity) retention time 2.5 m M -C2F4Cl 237 and
‡
235 (6 and 20), M C3F7 205, 203, and 201 (0.2, 1, and 2),
199 and 197 (1 and 3), 149 and 147 (3 and 9), 137 and 135 (3
and 9), 93 (7), 87 and 85 (12 and 35), 69(100). Retention
‡
time 2.6 m M -C2F4Cl 237 and 235 (7 and 23), 205, 203,

110
D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
and 201 (0.2, 1, and 2), 199 and 197 (1 and 4), 149 and 147 (4
and 12), 137 and 135 (4 and 12), 93 (7), 87 and 85 (14 and
46), 69 (100). HRMS (CI, CH4) calcd. for (MH HF)
C6F11Cl2 350. 9201; found 350.9193.
are presented. 19F NMR (282 MHz, CDCl3), 68.5 (t,
J ˆ 13 Hz, 2F), 81.6 (t, J ˆ 10 Hz, 3F), 120.5 (m,
2F), 121.5 (m 2F), 122.3 (m, 2F), 123.0 (m, 2F),
126.6 (m, 2F). IR (neat KBr, cm 1) 1369(w), 1319(w),
1237(s), 1212(s), 1149(s), 1067(w) 992(w), 784(w), 734(w),
677(w), 645(w), 570(w). GC-MS (rel. intensity) 219 (7), 187
and 185 (0.8 and 2.6), 181 (6), 169 (33), 147 (6), 137 and 135
‡
4.3. Ionic reactions
‡
4.3.1. Reaction of chorine with alkene 1 in tert-butyl
alcohol
(3 and 10), 131 (42), 119 (48), 116 (3), 100 (32), [CF2Cl]
87 and 85 (26 and 75), 69 (100).
To a 5.0 ml round bottom ¯ask with a Te¯on-coated
stirring bar was added 2.4 ml tert-butyl alcohol, 175 mg
(0.50 mmol) alkene 1, 8 mg mercuric acetate, 0.125 ml of
(2.0 M in carbon tetrachloride of 1-bromoper¯uorooctyl
bromide) internal standard. Oxygen gas was bubbled
through the mixture a 08 for 3 m, then chlorine gas until
the solution was saturated. The stopper was secured tightly
and the mixture stirred in the dark at room temperature for 2
weeks. Analysis by GC showed that ca. 11% of alkene 1 had
reacted, and that 1,2-dichloroper¯uoroheptane and 1-tert-
butoxy-2-chloroper¯uoroheptane were formed in a ratio of
25:1, respectively. The GC-MS and GC-FTIR agree with
that reported for these products isolated above. The dichlor-
oproduct was subjected to the reaction conditions for over 2
weeks and none of the t-butoxy-chloroproduct was
observed.
4.3.3. Reaction of chlorine with alkene 3 in methanol
To a 100 ml round bottom ¯ask with a Te¯on-coated
stirring bar was added 40 ml anhydrous methanol, 6.92 g
(0.020 mol) alkene 3 and 297 mg mercuric sulfate. Oxygen
was bubbled into the solution at 08 for 2 m followed by
chlorine gas until the solution was saturated. A Te¯on
stopper was secured to the ¯ask and the mixture stirred in
the dark for 72 h. The reaction in nitromethane as solvent
was carried out as above for 6 h without added catalyst. The
dichloro- and 2-chloro-1-methoxy products were resolved
on the GC, GC-MS, and GCFT-IR capillary columns, but
only partially resolved on the preparative GC column.
Spectral data below for 2-chloro-1-methoxy-1H,1H,2H-per-
¯uorooctane are taken from a mixture of the 2-chloro-1-
methoxy (>80%) and dichloro-products obtained by pre-
1
parative GC. HNMR (300 MHz, CDCl3) d ˆ 3:45 s, 3H),
4.3.2. Reaction of chlorine monofluoride with alkene 1 in
methylene chloride
3.72 (dd, J ˆ 11:0 and 7.3 Hz, 1H), 3.95(dd, J ˆ 11:0 and
3.9 Hz, 1H), 4.43(m, 1H). 13C (75.4 MHz, CDCl3) d ˆ 55:0
(t, J ˆ 22 Hz), 59.5(s), 70.8(brd. s). 19F (282 MHz, CDCl3)
d ˆ 81:3 (t, J ˆ 10 Hz, >3F due to minor dichloro pro-
duct), 116.0 (AB pattern, 2F), 120.7 (AB pattern, >2F),
122.3 (m, >2F), 123.3 (m, >2F), 126.6 (m, >2F). GC-
The reaction was carried out in a 300 cc 316 ss Parr
Instrument Co. stirred reactor as described in our earlier
paper [38]. To 3.50 g (0.010 mol) alkene 1 and 120 mL dry
methylene chloride at 08 was added 0.55 g (0.010 mol)
chlorine mono¯uoride. The stirred mixture was allowed
to warm to room temperature. After 1 h another 1.5 equiva-
lents of chlorine mono¯uoride was added since the reaction
was progressing slowly. The system was purged with nitro-
gen gas after a total of 2 h reaction time. Approximately,
100 ml of methylene chloride was removed by distillation
with a 15 cm 14/20 vigreux column. The undistilled mixture
was cooled to 108 and the bottom ¯uorocarbon layer
removed by pipette. Approximately, 20% of 1 had reacted
and the single product, 2-chloroper¯uoroheptane, was
obtained 99% pure by preparative GC. 19F NMR
(282 MHz, CDCl3) d ˆ 77:6 (ddd, J ˆ 20:4, 12.2 and
6.1 Hz, 3F), 81.2 (t, J ˆ 9:2 Hz, 3F), 116.7(m, 2F),
120.2(AB pattern, 2F), 123.0 (m, 2F), 126.5 (m,
2F), 138.5 (m, 1F). IR (neat KBr, cm 1) 1218(s),
929(w), 757(s) m 664(m).GC-MS (rel. intensity) 219
(11), 187 and 185 (2 and 6), 181 (5), 169 (12), 147 (9),
‡
MS (rel. intensity) M -OCH3 383 and 381 (0.05 and 0.2),
‡
131 (3), 119 (2), 100 (2), 69 (12), 63 (9), [CH3OCH2] 45
(100). GCFT-IR (gas, cm 1) 3010(w), 2940(w), 2837(w),
1345(w), 1243(s), 1140(m), 846(m), 810(w), 737(w).
4.3.4. Reaction of bromine or bromine monochloride with
alkene 3 in methanol
To 3.46 g (0.010 mol) alkene 3, 20 ml anhydrous metha-
nol, 15 mg mercuric sulfate when added, at 08 under oxygen
was added 1.6 g (0.010 mol) bromine or 0.010 mol of
bromine chloride as a 1.0 M solution in methylene chloride
(See footnote 6). The stopper was clamped to the 50 ml ¯ask
and its contents stirred in the dark at room temperature for 4±
9 days (Table 2). Analysis by GC gave the product distribu-
tions listed in Table 2. 2-Bromo-1-methoxy-1H,1H,2H-per-
¯uorooctane was isolated by water work-up, extraction with
pentane, and dried over anhydrous magnesium sulfate. The
product was distilled, bp 80±828 at 17 Torr, from several
combined reactions and found to be >98% pure by GC
analysis. 1HNMR (300 MHz, CDCl3) d ˆ 3:44 (s, 3H), 3.78
(dd, J ˆ 11:1 and 7.3 Hz, 1H), 3.96 (dd J ˆ 11:1 and
4.2 Hz,1H), 4.43 (tddt, J ˆ 13:4, 7.3, 42, and 1.1 Hz,
1H). 13C (75.4 MHz, CDCl3) d ˆ 44:8 (t, J ˆ 25:6 Hz),
59.4(s), 71.8 (brd. s). 19F (282 MHz, CDCl3) d ˆ 81:3
‡
[CF3CF=Cl] 137 and 135 (8 and 31), 131 (22), 119 (22),
116 (7), 100 (10), 87 and 85 (4 and 12), 69 (100). Authentic
samples of 2-chloroper¯uoroheptane and 1-chloroper¯uor-
oheptane were obtained from professor Lagow' laboratory.
The above data are identical to that obtained for the 2-
chloroproduct from professor Lagow. Spectral data for 1-
chloroper¯uoroheptane, not formed in the above reaction,

D.F. Shellhamer et al. / Journal of Fluorine Chemistry 106 (2000) 103±112
111
(t, J ˆ 10 Hz, 3F), 109.5 (dm, J ˆ 280 Hz, 1F), 114.3
(dm, J ˆ 280 Hz, 1F), 120.2 (AB pattern, 2F), 122.3 (m,
2F), 123.2 (m, 2F), 126.6 (m, 2F). GC-MS (rel. intensity)
Research Associates of PLNU (alumni support group).
The ionic reaction of chlorine mono¯uoride with per¯uor-
oheptene-1 was carried out at the laboratories of Air Pro-
ducts and Chemicals, Inc., Allentown, PA. We thank Dr.
Robert G. Syvret for his assistance with this reaction. We
would like to thank Dr. Rich Kondratt, at the Mass Spectro-
scopy Center, University of California, Riverside, for the
high resolution mass spectral data. The authentic samples of
1-chloro- and 2-chloroper¯uoroheptane from professor
Lagow's laboratory at the University of Texas at Austin
are greatly appreciated.
‡
M 458 and 456 (0.01 and 0.01), 457 and 455 (0.6 and 0.6),
M -Br 377 (0.2), 281 (2), 169 (1), 157 and 155 (1.0 and 1.0),
142 (2), 131 (5), 119 (4), 113 and 111 (3 and 2), 107 (6), 77
‡
1
(8), 69 (20), 63 (14), 51 (5), 45 (100). GCFT-IR (gas, cm
)
3003(w), 2936(w), 2833(w), 1346(w), 1242(s), 1142(w),
843(w), 810(w), 737(w). HRMS calcd. for M-1 C9H5F13BrO
456.9296; found 456.9292.
4.3.5. Reaction of iodine monochloride with alkene 3 in
methanol
The reaction was carried out (0.010 mol) as described
above for the ionic reaction of bromine in methanol.
Attempted puri®cation by distillation, column chromatogra-
phy, or crystallization led to decomposition. The following
data are from the crude reaction mixture with 1.0 equivalent
(0.010 mol) silver nitrate (Table 2). 2-Iodo-1-methoxy-
1H,1H,2H-per¯uorooctane by GC analysis contained
<10% volatile impurities. 1HNMR (300 MHz, CDCl3)
d ˆ 3:43 (s, 3H), 3.76 (m, 2H), 4.58 (m, 1H). 19F
(282 MHz, CDCl3) d ˆ 81:2 (t, J ˆ 9:7 Hz, 3F), 97.7
(dm, J ˆ 280 Hz, 1F), 110.7 (dm, J ˆ 280 Hz, 1F),
119.7 (AB pattern, 2F), 122.0 (m, 2F), 123.1 (m,
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Acknowledgements
Support for this work at Point Loma Nazarene University
was provided by the National Science Foundation (NSF-
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