Halogen displacement chemistry with silver and alkali metal salts: Preparation of SF5-esters, alcohols, aliphatic olefins, acids and an iodide

Article abstract of DOI:10.1016/j.jfluchem.2006.06.010

It has been found that treatment of SF₅-alkyl halides, especially SF₅(CH₂)₂Br, with silver salts such as CH₃C(O)OAg, p-CH₃C₆H₄SO₃Ag, CF₃SO_3<

Full text of DOI:10.1016/j.jfluchem.2006.06.010

Journal of Fluorine Chemistry 127 (2006) 1188–1194
www.elsevier.com/locate/fluor
Halogen displacement chemistry with silver and alkali metal salts:
Preparation of SF5-esters, alcohols, aliphatic olefins, acids and an iodide
*
R.W. Winter, G.L. Gard
Department of Chemistry, Portland State University, Portland, OR 97207, United States
Received 7 March 2006; received in revised form 22 May 2006; accepted 7 June 2006
Available online 15 June 2006
Abstract
It has been found that treatment of SF5-alkyl halides, especially SF5(CH2)2Br, with silver salts such as CH3C(O)OAg, p-CH3C6H4SO3Ag,
CF3SO3Ag and AgNO3 provides convenient pathways for preparing the following ester compounds: SF5CH2CH2R (R = CH3COO, TosO, CF3SO3,
NO3), SF5(CH2)3OTos, and SF5(CF2)4(CH2)2OAc. Important derivatives prepared from these esters include SF5(CH2)2OH; SF5(CF2)4(CH2)2OH.
Several alkenes SF5C(Br) CH2 and SF5CH2(COOCH3)C CHC(O)OCH3 are obtained using silver salts. The use of alkali metals salts with
SF5(CH2)3Br is studied and yields SF5(CH2)3I; also, a pathway has been developed that extends for SF5(CH2)3ꢀ the chain by two-carbon atoms and
also produces the first SF5-containing malonic acid.
Published by Elsevier B.V.
Keywords: SF5-esters; SF5-alcohols; Pentafluorothio (SF5); Silver and nucleophilic substituents; Sulfur hexafluoride derivatives
1. Introduction
of the silver salts with halogens (X = Br, I) gave the
corresponding SF5CH2Br [7,8] and SF5CF2I [9]. Several alkali
metal salts of SF5-carboxylic acids have also been reported
[10,11]. We have now found that silver salt anions can replace
the halide in various SF5-alkyl halides thereby considerably
expanding the range of reactivity of this readily available but
poorly reactive class of SF5-compounds. These method may be
advantageously used to prepare SF5-esters, alcohols, and
alkenes. In some instances alkali metal salts may be used in lieu
of silver salts.
The use of silver salts in chemistry often allows one to obtain
derivatives that cannot be prepared by other means. This
method allows the transfer of various groupings either to or
from silver salts. A recent survey covering the preparation and
reaction of perfluoroorganosilver(I) compounds has been
published [1]. There are several reports in the literature that
describe either the formation or use of silver and alkali metals
salts containing the SF5-group. The reaction of AgF with
SF5CF CF2 gave the isolatable salt, Ag(SF5CFCF3)ꢁCH3CN
[2]. The reaction of AgNO3 and SF5CBBCH produced a partially
characterized SF5CBBCAg salt [3]. The lithium salt, SF5CBBCLi
has been prepared in solution and was used to synthesize a
number of interesting SF5CBBCX (X = Hg, Cl, Br, I)
compounds [4]. The MSF5 salts (M = Ag, K, Rb, Cs,
(CH3)4, Cs(18-crown-6)2) were prepared from MF and SF4
[5]. The alkali metal and silver salts can be used to prepare
SF5Cl [6]. Silver salts of SF5-carboxylic acids have been
prepared by reacting the corresponding acid with silver
carbonate: SF5CX2C(O)OAg (X = H or F) [7–10]. The reaction
2. Results and discussion
In general, previous attempts to replace the halogen (X = Br,
Cl) in two-carbon SF5-alkyl halides have resulted in either no
reaction, elimination of XF or destruction of the SF5-group; for
example, treating SF5CH2CH2Br with NaI resulted in the
complete destruction of the SF5-group [12]. The purpose of this
study was to make direct use of the SF5-alkyl bromides or
iodides that are easily prepared using either SF5Br or
SF5(CF2)nI. For the compound SF5(CH2)3Br it was found that
the Br could be easily replaced; this is in sharp contrast with
SF5(CH2)2Br. This study also afforded an improved method for
making SF5-fluoroalkyl alcohols in high yields and a new
pathway for carbon chain extension in SF5-systems. A safe and
* Corresponding author. Fax: +1 503 725 9525.
E-mail address: gardg@pdx.edu (G.L. Gard).
0022-1139/$ – see front matter. Published by Elsevier B.V.
doi:10.1016/j.jfluchem.2006.06.010

R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
1189
effective method for preparing SF5CH2CH2Br is also given.
SF5CH2ðCOOCH3ÞCBrCH2COOCH3 þ AgOTos
This compound should not be prepared from SF5Br and
H2C CH2 under pressure and heat as carbonization will occur
[12].
CH3CN
ꢀ! SF5CH2ðCOOCH3ÞC¼CHCðOÞOCH3 þ AgBr
þ TosOH ð10Þ ðmp; 30ꢀ31 ꢂC; ꢃ 30%Þ
(10)
The following SF5-fluoroalkyl and SF5-alkyl esters have
been prepared by treatment of silver salts with the SF5-
fluoroalkyl and SF5-alkyl iodide or bromides; all but
SF5CH2CH2OTos are new compounds. SF5CH2CH2OTos
was previously prepared from SF5CH2CH2OH and p-
CH3C6H4SO2Cl [13]:
The silver salt acts as a base in these reactions with the
formation of AgBr and the corresponding acid; when bromine
is in the b-position to an acidic C–H bond, an elimination over
substitution reaction is apparently favored.
The starting SF5-compound in reaction (10) was prepared by
the following reaction which was carried out in CH2Cl2:
SF5CH2CH2Br þ AgOAc
CH2¼CðCOOCH3ÞCH2CðOÞOCH3 þ SF5Br
! SF5CH2CBrðCOOCH3ÞCH2CðOÞOCH3 ð11Þ
CHꢀC!OOHSF5CH2CH2OAc þ AgBr ð1Þ
3
ðbp; 50ꢀ52 ꢂC=10 Torr; 67%Þ
SF5CH2CH2Br þ AgOTfCꢀ6!H6SF5CH2CH2OTf þ AgBr ð2Þ
ðoil; 68%Þ
(1)
(2)
ðoil; 75%Þ
(11)
In addition to studying the chemistry of selected silver salts
with SF5 two-carbon halides, it was also of interest to look at
SF5 three-carbon halides. It was found that in SF5(CH2)3Br the
bromine could be substituted with tosyloxy and iodide.
Therefore, the SF5 three-carbon group is more stable and
readily transferable. This stability should allow the use of alkali
salts in preparing SF5-containing derivatives. Of great
importance was the development of a method for chain
elongation in SF5-alkanes. The following three-step reaction
scheme clearly demonstrates this new procedure:
SF5CH2CH2Br þ AgOTosCꢀH!3CNSF5CH2CH2OTos þ AgBr ð3Þ
ðmp54ꢀ55 ꢂC; 82%Þ
(3)
(4)
SF5CH2CH2Br þ AgONO2
CH3CN
ꢀ! SF5CH2CH2ONO2 þ AgBr ð4Þ ðoil; 70%Þ
SF5ðCH2Þ3Br þ AgOTosCꢀH!3CNSF5ðCH2Þ3OTos þ AgBr ð5Þ
SF5ðCH2Þ3Br þ KCHðCOOCðCH3Þ3Þ2
ðoil; 87%Þ
(5)
! SF5ðCH2Þ3CHðCOOCðCH3Þ3Þ2 þ KBr ð12Þ
ð ꢃ 100%Þ
(12)
SF5ðCF2Þ4ðCH2Þ2I þ AgOAc
CHꢀC!OOHSF5ðCF2Þ ðCH2Þ OAc þ AgI ð6Þ ðoil; 84%Þ (6)
3
SF5ðCH2Þ3CHðCOOCðCH3Þ3Þ2 þ HClðaqÞ
4
2
! SF5ðCH2Þ3CHðCOOHÞ2 þ ðCH3Þ2C¼CH2 þ H2O ð13Þ
When the following SF5-esters were transesterified, the corre-
sponding alcohols were prepared in high yields:
ðsemi-solid; 86%Þ
(13)
170 ꢂ
C
i
SF5ðCH2Þ3CHðCOOHÞ2 ꢀ! SF5ðCH2Þ4COOH þ CO2 ð14Þ
SF5CH2CH2OAcꢀ! SF5CH2CH2OH;
2i
ð80ꢀ85 ꢂC=70ꢀ90 mm; 60%Þ
(14)
ðiÞ cat: amt: NaOCH3 in CH3OH; ð2iÞ aq: HCl ðtraceÞ ð7Þ
ðbp73 ꢂC=50 Torr; 79%Þ
(7)
In contrast to SF5(CH2)2Br, the three-carbon chain survived
treatment with NaI:
i
SF5ðCH2Þ Br þ NaIacꢀe!toneSF5ðCH2Þ I þ NaBr ð15Þ
SF5ðCF2Þ4ðCH2Þ2OAcꢀ! SF5ðCF2Þ4ðCH2Þ2OH;
2i
3
3
ð46ꢀ47 ꢂC=5 Torr; 73%Þ
(15)
ðiÞ cat: amt: NaOCH3 in CH3OH; ð2iÞ aq: HCl ðtraceÞ ð8Þ
ðoil; 69%Þ
An important outcome of the above method is that SF5-contain-
ing alcohols are readily prepared in high yields and purity. The
alcohol SF5CH2CH2OH was previously prepared from SF5Cl
and ketene followed by reduction of SF5CH2C(O)Cl with
LiAlH4 [13], while SF5(CF2)2(CH2)2OH was prepared by the
laborious lactam method [14].
(8)
The infrared spectra for the new compounds exhibit strong
absorption bands in the 800–900 cmꢀ1 range due to the S–F
stretching modes of the SF5-group. The C–H stretching bands
were located near 3000 cmꢀ1. The carbonyl stretching band for
compounds 1, 6, 11, 12, and 14 is located in the range 1714–
1752 cmꢀ1
.
The mass spectral peaks contained, for some of the
compounds, a parent ion but all compounds had peaks
supporting the assigned structures.
An interesting observation was made when the following
two SF5Br–olefin adducts were treated with silver salts:
1
The H and 19F NMR spectral data for all new compounds
SF5CHBrCH2Br þ AgOAc
are given in Section 3. The compounds show a typical AB4
splitting pattern in the 19F NMR spectrum for the SF5-group.
Except for SF5(CF2)4(CH2)2OOCCH3 (6), the axial fluorine (A)
for the new SF5-acids and esters appears as a nine line pattern
CHꢀC!OOHSF5CðBrÞ¼CH2 þ AgBr þ CH3COOH ð9Þ
3
ð72%Þ
(9)

1190
R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
+
+
and is located in the range 80–86 ppm; for (6) the axial fluorine
appears at 65.0 ppm. The equatioral fluorines (B), except for
(6), appear as a doublet of multiplets in the range of 64–66 ppm;
for (6) the axial fluorine is found at 45.0 ppm. The values for
these compounds and for the remaining SF5-compounds are in
excellent agreement with analogous SF5-compounds [15].
SF2 ; 51, 2, SF+; 47, 52, (C2H4F)+, (SCH2 + H)+; 28, 13, C2H4 ;
+
27, 80, C2H3 ; 26, 12, C2H2 .
+
3.2. SF5CH2CH2OOCCH3 (1)
SF5CH2CH2Br (1.11 g, 4.72 mmol), CH3COOAg (0.90 g,
5.4 mmol) and 10 ml of glacial acetic acid were heated in a
25 ml round bottom flask containing a stirring bar to reflux for 5
days. AgBr was filtered off, the filtrate was poured into 100 ml
of water and the product extracted with ether (1ꢄ 20, 2ꢄ
10 ml). Distillation affords 0.68 g of a colorless liquid,
bp = 50–52 8C/10 Torr, yield = 67%. The time of refluxing
could be halved by adding about 1 g of potassium acetate for
every 6 g of silver acetate (to increase the solubility of silver
acetate).
1H NMR spectrum: d1 = 4.49 ppm, t (each band shows signs
of additional (pentet) splitting), Jt = 6.10 Hz, Jp ꢃ 1 Hz, 2H
(CH2O); d2 = 3.91, t–p, Jt = 6.10, Jp = 7.85, 2H (SF5CH2);
d3 = 2.10, s, 3H (CH3CO).
19F NMR spectrum: (AB4-type) dA = 80.3 ppm, nine lines,
1F; dB = 66.0, skewed d, 4F, JAB = 148 Hz.
3. Experimental
The reactant SF5Br was prepared from SF4, BrF3, Br2 and
CsF via a method previously described by our laboratory [16].
The compounds SF5(CH2)3Br [15], SF5(CF2)4(CH2)2I [17] and
SF5CHBrCH2Br [3] were prepared according to the literature
method. SF5CH2CH2Br was first prepared by Merrill [18]. We
have modified his method in order to prepare larger amounts in
a safe and facile manner.
The infrared spectra of the reactants and products were
obtainedona Perkin-Elmer 2000 FTIR spectrometer operating at
1.0 cmꢀ1 resolution using KBr windows. The NMR spectro-
scopy values were obtained by use of the following instruments:
19F Varian EM-390 (84.7 MHz) and 1H General Electric
(500 MHz) in CDCl3 with CCl3F and Si(CH3)4 as internal
standards. Gas chromatography–mass spectroscopy (GC–MS)
results were obtained using a Hewlett-Packard HP5890 mass
selective detector (operating at 70 eV) and a DB5, 30 m column;
the temperature profile used was 50 8C for 2 min, then
11 8C minꢀ1 up to 280 8C. The HRMS values were determined
on a Kratos MS 50TC; chemical ionization with methane.
Infrared spectrum (KBr): 3034, w; 2986, w; 1752, vs; 1720,
sh, s; 1466, sh, m; 1419, m; 1393, m; 1371, m–s; 1310, w; 1286,
sh, m–s; 1241, s–vs; 1084, br, w–m; 1051, s; 1004, w; 978, w–
m; 944, w; 839, vs; 812, s; 712, w; 635, w–m; 604, m; 586, w–
m; 565, w–m; 553, m.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 4.33 min, 137, 1, (SF4CH2CH2 + H)+; 133, SF4C2H+;
+
127, 8, SF5 ; 122, <1, SF4CH2 ; 89, 11, SF3 ; 87, 11,
+
+
+
+
3.1. SF5CH2CH2Br
CH2CH2OOCCH3 ; 70, 1, SF2 ; 61, 2, (SCH2CH2 + H)+; 47, 9,
(SCH2 + H)+; 43, 100, CH3CO+.
An acid-washed and very dry 3 l surge-vessel with a
cylindrical extension at one end (finger) and a Teflon stopcock
at the other end was charged by vacuum-condensation (liquid
nitrogen) with ethylene and then SF5Br so that their combined
pressure at room temperature would be 1 atm (a slight excess of
ethylene was used). The vessel was slowly warmed to room
temperature; a reaction was noticed by a wetting of the walls,
fog formation and a steady increase of the volume of liquid
collecting in the cylindrical finger of the vessel. After several
hours, the product is transferred into a cold-trap. If the vessel
had been properly dried and the SF5Br was of good quality, the
product would be pure and obtained in practically quantitative
yield. However, it is recommended that the product
(bp = 108 8C) is distilled because of the frequent presence of
trace quantities of SF4 which would lead to etching of glass
containers upon storage.
Anal. calcd. for C4H7F5O2S: C, 22.43; H, 3.29; F, 44.4; S,
14.97. Found: C, 22.72; H, 3.32; F, 44.0; S, 14.91.
3.3. SF5CH2CH2OSO2CF3 (2)
SF5CH2CH2Br (4.15 g, 17.7 mmol) and silver triflate
(6.65 g, 25.9 mmol) in 50 ml of benzene were heated in a
30 ml Carius tube in an oil bath at 115–120 8C for a total of 3
weeks; a gradual darkening occurred during heating. AgBr was
filtered (2.63 g, 79%) and the benzene evaporated (rotary
evaporator); the product was taken up in 50 ml of methylene
chloride (a salt is precipitated) and passed through 5 g of
Kieselgel and after re-evaporation, 3.63 g (68%) of a brown
clear, oily compound was obtained, and found to be virtually
pure by GC–MS analysis. When (2) is distilled under high
vacuum a colorless oil is found; at ambient temperatures a
yellow cast is quickly formed.
1H NMR spectrum: d1 = 3.74 ppm, m, 2H (CH2Br);
d2 = 4.06, m, 2H (SF5CH2).
1H NMR spectrum: d1 = 4.86 ppm, t, J12 = 6.0 Hz, 2H;
d2 = 4.02, t–p, JSF CH = 7.6, J = 6.0, 2H.
19F NMR spectrum: (AB4-type) dA = 78.6 ppm, nine lines,
1F; dB = 67.4, skewed d–m, 4F, JAB = 150 Hz.
4
2
19F NMR spectrum: (AB4-type) dA = 80.0 ppm, nine lines,
Infrared spectrum (KBr): 3059, vw; 3030, vw; 2983, vw;
1752, vs; 141434, w–m; 1314, w; 1279, w; 1223, w–m; 1145,
977, w–m; 927, w–m; 828 (vs with sh at 828); 584, vs.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 2.31 min, 236, 234, 5%, 5%, M(81Br, 79Br)+; 127, 28,
1F; dB = 66.0, skewed d, 4F, JAB = 147 Hz; ’CF = ꢀ75, s, 3F.
3
Infrared spectrum (KBr): 3037, w; 2986, w; 1752, w–m;
1420, vs; 1339, vw; 1277, sh, w; 1248, s–vs; 1219, s–vs; 1145,
s–vs; 1084, w–m; 1054, vw; 1006, s; 975, s; 926, m–s; 898, sh,
m; 834, vs; 795, m–s; 755, m–s; 706, vw; 676, w; 641, sh, m;
615, s; 591, m; 579, w–m; 566, m; 554, m–s; 526, m.
SF5 ; 109, 107, 97%, 100%, (M ꢀ SF5)+; 89, 38, SF3 ; 70, 11,
+
+

R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
1191
Mass spectrum (70 eV: ion (m/z), %, assignment):
(M ꢀ SF5)+;
High-resolution mass spectrum calcd. for 12C2H519F5
Rt = 4.13 min,
177,
2,
165,
4,
16O332S14N (MH+): 217.99104. Found: 217.99087.
(CF3SO2OCH2 + 2H)+; 135, 9, C2H3SF4 ; 133, 9, CF3SO2 ,
+
+
+
+
C2HSF4 ; 127, 27, SF5 ; 101, 16, CF3S+; 99, 10,
3.6. SF5CH2CH2CH2OTos (5)
+
+
(C2H4SF2 + H)+; 89, 29, SF3 ; 69, 100, CF3 ; 47, 44,
(CH2S + H)+.
SF5CH2CH2CH2Br (1.00 g, 4.0 mmol), silver tosylate
(2.10 g, 7.2 mmol) and acetonitrile (10 ml) were heated in
30 ml Carius tube in a boiling water bath for 9 h. The product
was isolated as described for SF5CH2CH2OTos and obtained as
an oil (1.19 g) in 87% yield.
High-resolution mass spectrum calcd. for 12C3H519F832S2
16O3 (MH+): 304.95523. Found: 304.95322.
3.4. SF5CH2CH2OTos (3)
1H NMR spectrum: d1 = 4.10 ppm, t, Jt = 5.7 Hz, 2H
(CH2O); d2 = 2.28, ꢃt–t (broadened), J ꢃ 5.7, J ꢃ 7.7 Hz,
2H (C–CH2–C); d3 = 3.72, t–p (or septet), Jt = 7.8, Jp = 7.8, 2H
(SF5CH2); d4 = 2.46, s, 3H (CH3C6H4); d = 7.37, d, 2H;
d = 7.78, d, 2H, J = 8.20 (toluyl).
SF5CH2CH2Br (8.01 g, 34.1 mmol), silver tosylate (15.0 g,
35.8 mmol) and acetonitrile (20 ml) were heated in a 30 ml
Carius tube in a boiling water bath for 9 h. AgBr was filtered
away and the filtrate was poured into water (100 ml); the
product was extracted with ether (3ꢄ 30 ml). The solvent was
removed and the crude product passed through 20 g of
Kieselgel in CH2Cl2. The solvent was removed and 9.05 g
of an oil was obtained; the oil slowly solidified. mp = 54–55 8C,
reported, 56 8C [13]. Yield = 81.5%.
19F NMR spectrum: (AB4-type) dA = 84.7 ppm, nine lines,
1F; dB = 65.2, skewed d, 4F, JAB = 150 Hz.
Infrared spectrum (KBr): 3068, vw; 3040, vw; 2975, w;
2925, w; 2865, vw; 1599, 1496 w–m; 1471, w–m; 1450, w–m;
1434, w–m; 1399, w–m; 1361 (s with sh at 1389); 1308, w–m;
1295, w–m; 1252, w; 1215, w; 1191, s; 1178, s; 1120, w; 1098,
m; 1076, w; 1042, vw; 1019, w–m; 985, w–m; 934, s; 831 (vs
with sh at 868); 816, vs; 770, w–m; 742, m; 702, vw; 686, w–m;
663, s; 633, s; 600, s.
1H NMR spectrum: d1 = 4.40 ppm, t, Jt = 6.25 Hz, 2H
(CH2O); d2 = 3.91, t–p, Jt = 6.25, Jp = 7.81, 2H (SF5CH2);
d3 = 2.10, s, 3H (CH3C6H4). d = 7.38, d, 2H; d = 7.80, d, 2H,
J = 8.20 (toluyl).
19F NMR spectrum: (AB4-type) dA = 81.4 ppm, nine lines,
1F; dB = 66.2, skewed d, 4F, JAB = 146 Hz.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 17.2 min, 340, 22, M+; 213, <1, (M ꢀ SF5)+; 185, 3,
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 15.71 min, 326, 31, M+; 172, 2, TosOH+; 155, 87,
TosOCH2 ; 172, 14, TosOH+; 155, 100, Tos+; 127, 1, SF5 ; 107,
+
+
8, C2H3SO3 ; 91, 90, C7H7 ; 89, 10, SF3 ; 77, 2, C2H2SF+; 65,
16, CH2SF+; 51, 2, SF+; 41, 5, C3H5 ; 39, 3, C3H3 .
+
+
+
+
(M ꢀ TosO)+; 133, 5, SF3CH2CH2O+; 107, 8, C2H3SO3 ; 91,
+
+
+
+
100, C7H7 ; 89, 9, SF3 ; 77, 3, C2H2SF+; 65, 19, CH2SF+; 51, 2,
12
High-resolution mass spectrum calcd. for
16O332S2: 340.02263. Found: 340.02244.
C
1H1319F5
10
SF+; 39, C3H3 .
+
3.5. SF5CH2CH2NO3 (4)
3.7. SF5CF2CF2CF2CF2CH2CH2OOCCH3 (6)
SF5CH2CH2Br (2.45 g, 10.4 mmol), 10 ml of CH3CN and
AgNO3 (6.8 g, 140.5 m.f.w.) were heated in a 30 ml Carius tube
at 100 8C for 5 h. After filtration, the filtrate was poured into
100 ml of water, and the product was extracted with ether (3ꢄ
20 ml). The combined extracts were washed once with 10 ml of
water and then dried over Na2SO4. The product was
concentrated under vacuum; 1.63 g of a colorless, slightly
oily product (72%) was obtained. Further distillation was not
attempted.
1H NMR spectrum: d1 = 4.88 ppm, t, Jt = 6.1 Hz, 2H
(CH2O); d2 = 3.97, t–p, Jt = 6.1, Jp = 7.63, 2H (SF5CH2).
19F NMR spectrum: (AB4-type) dA = 81.0 ppm, nine lines,
1F; dB = 66.0, skewed d, 4F, JAB = 146 Hz.
Infrared spectrum (KBr): 3039, w–m; 2987, w; 2917, w–m;
2666, w–vw; 2560, w; 2385, w; 2257, w; 1652, vs; 1465, m;
1437, m; 1419, m–s; 1388, w; 1335, w–m; 1284, s; 1227, w;
1216, w; 1083, w–m; 1071, w–m; 1030, m; 1000, m; 898, sh, m;
837, vs; 756, m; 737, w; 706, w; 674, w; 648, br, w; 605, w–m;
587, w–m; 565, w–m; 550, w–m.
SF5CF2CF2CF2CF2CH2CH2I (1.00 g, 2.1 mmol), silver
acetate (0.40 g, 2.4 mmol) and 3 ml of glacial acetic acid
were heated (116 8C) for 30 min in a 10 ml round bottom flask.
After filtration (0.496 g AgI), the product was isolated as above,
except that methylene chloride was used to extract the aqueous
phase. The crude product dissolved in CH2Cl2 was passed
through 5 g of Kieselgel and after evaporation gave 0.72 g of a
colorless oil (84%).
1H NMR spectrum: d1 = 4.38 ppm, t, Jt = 6.71 Hz, 2H
(CH2O); d2 = 2.45, t–t, J = 6.61, J = 18.3 Hz, 2H (CF2CH2);
d3 = 2.08, s (CH3CO).
19F NMR spectrum: (SF5: AB4-type) dA = 65.0 ppm, nine
lines, each line with triplet splitting, 1F; dB = 45.0, skewed d,
4F, JAt ꢃ 4.9, JAB = 152 Hz. CF2: d3 = ꢀ116, ꢃp, J = 18 Hz, 2F
(CF2CH2); d4+5 = ꢀ125, m, 4F; d6 = ꢀ96, ꢃp, Jp ꢃ 16, 2F; J6A
not resolved.
Infrared spectrum (KBr): 2976, w; 2917, vw; 1752, s; 1479,
vw; 1463, w; 1431, w; 1397, vw; 1327, w–m; 1222, s; 1198, sh,
m–s; 1170, m; 1148, s; 1108, w–m; 1074, w–m; 1053, w–m;
1014, w; 967, vw; 959, vw; 883, vs; 821, w; 789, m; 752, w–m;
742, w–m; 732, w; 722, w; 710, w; 695, m; 685, w–m; 668, vw;
603, w; 585, vw.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 3.78 min, 151, <1%, (M ꢀ NO2–H–F)+; 133, 5, SF4C2H+;
+
127, 12, SF5 ; 122, 6, SF4CH2 ; 108, <1, SF4 ; 89, 20, SF3 ;
+
+
+
76, 4, SC2H4O+; 70, 4, SF2 ; 46, 100, NO2 .
+
+

1192
R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
+
C4H2F5 ; 131, 15, C3F5 ; 127, 18, SF5 ; 119, 20,
+
+
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 6.91 min, 414, 4, M+; 394, 3, (M ꢀ HF)+; 227, 10,
(C2F4 + F)+; 100, 12, C2F4 ; 95, 57, CF2CH2CH2OH+; 89,
+
29, SF3 ; 77, CF2CH2CH+; 69, 16, CF3 ; 65, (CF2CH2 + H)+;
+
SF5CF2CF2 ; 177, 2, SF5CF2 ; 127, 5, SF5 ; 95, 10,
+
+
+
+
+
+
(CF2CH2CH2O + H)+; 89, 10, SF3 ; 77, 14, CF2C2H3 ; 73,
51, 9, SF+; 31, 100, CH2OH+.
+
1
19
13, C3H2FO+; 69, 8, CF3 ; 51, 3, SF+; 43, 100, CH3CO+.
High-resolution mass spectrum calcd. for 12C6 H6
F
13
1
19
High-resolution mass spectrum calcd. for 12C8 H7
F
13
16O32S (MH): 372.99318. Found: 372.99306.
16O232S: 413.99592. Found: 413.99567.
3.10. SF5CBr CH2 (9)
3.8. SF5CH2CH2OH (7)
Silver acetate (5.3 g, 0.032 f.w.), 4.81 g of SF5CHBrCH2Br
(4.81 g, 0.0153 mol) and glacial acetic acid (15 ml) were
refluxed in a 50 ml round bottom flask for 4 days. The cooled
supernatant portion was poured into water (20 ml) producing
2.6 g of pure 1-SF5–1-Br–ethylene; yield was 72%. A sample
for analysis was obtained by preparative gas chromatography
on an SE-30 column, length 3 m, at 140 8C. The infrared
spectrum of this compound was identical to that of an authentic
sample of SF5CBr CH2 [3].
A solution of SF5CH2CH2OOCCH3 (2.50 g, 11.7 mmol) in
methanol (10 ml) was made weakly alkaline (pH 9–10) by
adding dropwise a solution of Na in methanol (15 mg/ml). After
standing at ambient temperature for 18 h the solution was
neutralized by adding a drop of dil. HCl (6N); methanol and
methyl acetate were removed by distillation at atmospheric
pressure. The product (1.58 g, 79%) was obtained by
distillation at 73 8C/50 Torr. The literature boiling point is
77 8C/49 Torr [17].
1H NMR spectrum: d1 = 4.09 ppm, t–p, J12 = 6.0 Hz,
J1SF ꢃ 1, 2H; d2 = 3.87, t–p, J = 6.0, J2SF = 8.5, 2H.
3.11. Dimethyl SF5-citraconate (10)
4
4
19F NMR spectrum: (AB4-type) dA = 84.0 ppm, nine lines,
1F; dB = 65.5, skewed d, 4F, JAB = 144 Hz.
Dimethyl a-bromo-a-(SF5-methyl) succinate (1.12 g,
3.07 mmol, 11), silver tosylate (7.63 g, 27.3 mmol) and
15 ml of acetonitrile were heated in a 30 ml Carius tube at
110–120 8C for 5 h. After filtration and pouring the filtrate into
water (100 ml), the product was extracted with ether (3ꢄ
30 ml). The ether was distilled away and the product (0.84 g)
was heated under dynamic vacuum in a short-path distillation
unit and condensed in a cooled receiving flask to give 0.61 g of
a partially crystalline product. The product was then re-
crystallized from cyclohexane at +4 8C; mp = 30–31 8C.
Yield = 70%.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 2.67 min, 171, ꢅ1%, (M ꢀ H)+; 152, 6, (M ꢀ HF)+;
151, 10, (M ꢀ H–HF)+; 127, 17, SF5 ; 122, 63, SF4CH2 ; 89,
+
+
100, SF3 ; 70, 15, SF2 ; 65, 7, SFCH2 ; 51, 4, SF+; 45, 92,
SCH+, C2H5O+; 44, C2H4O+; 43, C2H3O+; 31, 40, CH2OH+; 29,
+
+
+
+
+
23, C2H5 , COH+; 27, C2H3 .
3.9. SF5CF2CF2CF2CF2CH2CH2OH (8)
A solution of SF5CF2CF2CF2CF2CH2CH2OOCCH3 (0.50 g,
1.21 mmol) in 5 ml of methanol (ꢃ170 mmol) was made
alkaline by adding dropwise a solution of 1.6 mg Na in 1 ml of
methanol. The reaction was completed after 1 h. A drop of HCl
(6N) was then added and the solvent removed; the residue was
taken up in methylene chloride and passed through a short
column of Kieselgel. The solvent was removed by evaporation;
0.31 g (69%) of the pure compound (oil) was found.
1H NMR spectrum: d1 = 4.0 ppm, t, J12 = 6.4 Hz, 2H
(CH2OH); d2 = 2.5, t–t–t, J23 = 19.0, J12 = 6.4, J24 ꢃ 0.8
(poorly resolved), 2H, CF2CH2).
1H NMR spectrum: d12 = 3.82, s, 3H; d12 = 3.87, s, 3H
(CH3); d3 = 5.26, p, J = 6.70 Hz, 2H (CH2SF5); d4 = 7.07, s, 1H
(CH C).
19F NMR spectrum: (AB4-type) dA = 81.7 ppm, nine lines,
1F; dB = 67.2, skewed d, 4F, JAB = 150 Hz.
Infrared spectrum (KBr): 3054, w; 3009, w–vw; 2962, w–m;
2850, vw; 1738, 1734, vs; 1653, w–m; 1440, s, sh at 1459,
1428; 1368, m; 1287, s–vs; 1254, m; 1240, s; 1205, s–vs; 1185,
m–s; 1101, m–s; 1069, vw; 1022, m–s; 981, vw; 937, w–m; 921,
w–m; 863, s–vs; 846, vs; 827, vs; 791, s–vs; 751, vw.
Mass spectrum (70 eV: ion (m/z), %, assignment): 252,
100%, (M ꢀ CH3OH)+; 157, 30, (M ꢀ SF5)+; 145, 35,
19F NMR spectrum: (AB4-type) dA = 64.2 ppm, nine lines
(poorly resolved), 1F; dB = 44.6, skewed d, 4F, JAB = 142 Hz
(broad FA-signal, needed for determination of JAB, allowed for
little accuracy). CF2: d3 = ꢀ116, not resolved, 2F (CF2CH2);
+
+
(M ꢀ SF5 + 2H)+; 127, 8, SF5 ; 117, 14, C7HO2 ; 98, 20,
+
+
(C5H6O2)+; 89, 20, SF3 ; 59, 35, COOCH3 .
Anal. calcd. for C7H9F5O4S: C, 29.58; H, 3.19; F, 33.43.
Found: C, 29.88; H, 3.35; F, 33.3%.
d
4+5 = ꢀ125, not resolved, 4F; d6 = ꢀ96, not resolved, 2F.
Infrared spectrum (KBr): 2976, w; 2917, vw; 1752, s; 1479,
sh, vw; 1463, w; 1431, w; 1397, vw; 1372, w–m; 1222, s; 1198,
m–s, sh; 1170, m; 1148, s–vs; 1108, w–m; 1074, w–m; 1053,
w–m; 1014, w; 967, vw; 959, vw; 883, vs; 822, w; 789, w–m;
762, w–m; 742, w–m; 722, w; 709, w; 695, w–m; 684, w–m;
668, w; 603, w.
3.12. Dimethyl a-bromo-a-(SF5-methyl) succinate (11)
Dimethyl itaconate (6.33 g, 40.0 mmol), methylene chloride
(25 ml) and SF5Br (8.77 g, 42.4 mmol) were heated together at
69–72 8C for 20 h in a 75 ml steel bomb vessel. Distillation of
the mixture under reduced pressure gave 10.94 g (75%) of a
light-tan oily product (11); bp = 85–95 8C/0.5–1 Torr. The
compound was used for preparing compound (10).
Mass spectrum (70 eV: ion (m/z), %, assignment): 371,
<1%, (M ꢀ H)+; 252, 5, (M ꢀ HF)+; 195, 11, (M ꢀ SF5CF2)+;
175, 9, (M ꢀ HF–SF5CF2)+; 157, 6, C5H2F5 ; 145, 10,
+

R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
1193
1H NMR spectrum: db1 = 3.75 ppm, d, 1H; db2 = 3.88, d, 1H,
0
Jb1b2 = 18.6 Hz (CH2CO); db 1 = 4.70, d–p, 1H, Jb1b2 = 14.7,
with CH2Cl2 (3ꢄ 15 ml), leaving 0.69 g of solid after
concentration. This solid was crystallized twice from CH2Cl2.
Analysis of the product by GC–MS showed that compound
(13) was not stable in the gas chromatography unit (heated
injection block) and had decomposed to product (14).
19F NMR spectrum: (AB4-type) dA = 85.5, nine lines, 1F;
dB = 64.2, JAB = 147.3 Hz (AB4-system).
0
SF b1 = 7.8; db 2 = 5.05, d–p, JSF b1 = 8.2, 1H; dCH = 3.75, s,
J
3H; dCH = 3.88, s, 3H.
4
4
3
3
19F NMR spectrum: (AB4-type) dA = 82.5 ppm, nine lines,
1F; dB = 67.8, skewed d, 4F, JAB = 146 Hz.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 12.82 min, 364, 366, <1%, M+; 333, 335, 22, 22,
(M ꢀ OCH3)+; 253, 14, (M ꢀ HBr–OCH3)+; 193, 195, 38,
Anal. calcd. for C6H9F5O4S: C, 26.48; H, 3.33; S, 11.78.
Found: C, 27.20; H, 3.22; S, 11.19.
38, (M ꢀ SF5CH2–OCH3 + H)+; 157, 16, (M ꢀ SF5–Br + H)+;
145,
21,
SF4C3H+;
127,
19,
99,
53,
3.15. SF5CH2CH2CH2CH2COOH (14)
+
SF5 :
+
+
(CH3OOCCH2CCH2 C5H7O2)+; 89, 12, SF3 ; 71, C3H3O2 ;
+
+
59, 100, C2H3O2 ; 51, 6, SF+; 39, 20, C3H3 .
The combined impure malonic acid fractions from the
previous step (3.8 g) were heated in a 25 ml distillation flask
(oil-bath) with stirring to 167 8C. Initially, bubbling was
observed at 140 8C, and then heating was continued from 140 to
167 8C over a 20 min period; the reaction was then heated at
167 8C for 10 min. Distillation under a dynamic vacuum at 80–
85 8C (70–40 mm) gave 2.10 g of a colorless oily liquid.
1H NMR spectrum: da = 2.43 ppm, t, J = 7.23 Hz, 2H; db,
dg = 1.70, m, 2H and 1.97, m, 2H; dd = 3.68, t–p, JBd = 8.20,
Jgd ꢃ 7, 2H.
High-resolution mass spectrum calcd. for 12C7H1119F5
32S16O479Br (MH)+: 364.9482. Found: 364.9497.
3.13. SF5CH2CH2CH2CH(COOC(CH3)3)2 (12)
KOC(CH3)3 (2.28 g, 19.5 mmol) was added to 50 ml of
ethyleneglycol dimethylether in a 100 ml round bottom flask
and stirred for ꢃ0.5 h; di-t-butyl malonate (4.00 g, 18.5 mmol)
was added and stirring continued in a water bath for 0.25 h.
SF5(CH2)3Br (4.46 g, 17.9 mmol, in 10 ml of (CH3OCH2)2)
was added dropwise to this solution over a 0.5 h period. After
1.5 h, an additional 0.10 g of KOC(CH3)3 was added; this
addition was repeated again after 1.5 h. The solution was
yellow and after 0.25 h was filtered; the solvent was removed
under vacuum, leaving behind 7.03 g of a yellowish oil that was
used in preparing compound (13).
19F NMR spectrum: (AB4-type) dA = 85.7, nine lines, 1F;
dB = 64.3, JAB = 148 Hz (AB4-system).
Infrared spectrum (KBr): 2974, vb–m; 1714, vs; 1467, w–m;
1433, m; 1418, m; 1290, m; 1266, m; 1240, w; 1212, m; 1157,
w–m; 1083, w–m; 915, sh, m; 870, sh, s–vs; 825, vs; 751, m;
690, m; 683, s.
Mass spectrum (70 eV: ion (m/z), %, assignment):
+
1H NMR spectrum: dCH = 1.47, s, 18H; da = 3.15, t,
Rt = 9.66 min, 211, <1%, (M ꢀ OH)+; 127, 8, SF5 ; 108,
3
<1, SF4 ; 101, 15, (M ꢀ SF5)+; 99, 10, (M ꢀ SF5–2H)+; 89, 22,
+
J
dd = 3.68, t–p, Jgd = 8.01, JBd = 8.20, 2H.
ab = 7.42 Hz, 1H; db = 1.85, m, 2H; dg = 1.98, m, 2H;
SF3 ; 83, 38, (M ꢀ SF5–OH–H)+; 73, 7, C3H5O2 ; 70, 6, SF2 ;
+
+
+
19F NMR spectrum: (AB4-type) dA = 85.2, nine lines, 1F;
dB = 64.5, JAB = 148 Hz (AB4-system).
59, C2HO2 ; 55, 100, C3H3O+; 41, 29, C3H5 , C2HO+.
Anal. calcd. for C5H9F5O2S: C, 26.32; H, 3.98; F, 41.63; S,
14.05. Found: H, 26.24; H, 3.86; F, 41.3; S, 14.15.
+
+
Infrared spectrum (KBr): 3004, m; 2981, s; 2938, m; 2894,
sh, w; 1726, vs; 1478, m; 1460, m; 1413, w; 1394, m–s; 1370, s–
vs; 1349, m; 1296, s; 1284, s; 1256, s–vs; 1164, sh, s–vs; 1142,
vs; 1072, m; 1041, m; 973, w; 929, vw; 877, s–vs; 838, vs; 740,
w–m; 684, vw; 660, vw; 629, m–s; 596, m; 568, m.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 14.52 min, 313, 5, (M ꢀ (CH3)2C CH2–CH3)+; 273, 8,
(M ꢀ (CH3)3CO–2F)+; 228, 2, (CH2CH(COOC(CH3)3)2–H)+;
3.16. SF5CH2CH2CH2I, g-SF5-propyl iodide (15)
Into a 100 ml flask, 10.2 g of NaI (68 mmol) and 75 ml of
acetone were added. The flask was wrapped with Al-foil and
5.10 g of SF5CH2CH2CH2Br (21 mmol) was added dropwise.
A precipitate quickly formed and after 100 min the reaction was
complete. The complex, NaIꢁ(CH3)2C O was filtered away by
suction filtration, washed with cold acetone, and the filtrate
poured into 0.4 l of ice-water. The product was extracted with
1ꢄ 75, 2ꢄ 20 ml of CH2Cl2, and the combined extracts were
washed with water (1ꢄ 80 ml). The extract was dried
(Na2SO4). Distillation resulted in 4.42 g (73%) of product,
bp = 46–47 8C/5 Torr.
145, 10, (C6H8O2S + H)+; 127, 3, SF5 ; 115, 6,
+
+
+
(CHCOOC(CH3)3 + H)+; 89, 1, SF3 ; 57, 100, C4H9 ; 41,
+
16, C3H3 .
3.14. SF5CH2CH2CH2CH(COOH)2 (13)
The crude di-t-butyl g-SF5-propylmalonate (12) from the
previous reaction (7.03 g, ꢆ17.9 mmol) was heated with 25 ml
of concentrated HCl at 70–80 8C for 70 min in a 50 ml round
bottom flask; gas evolution was apparent even at the warm-up
stage. The solution was kept in an ice-bath for 1 h, and the
crystalline precipitate filtered away. In an attempt to re-
crystallize from a warm aqueous acetone solution, gas evolution
and formation of an insoluble oil occurred. The oil (3.51 g) was
recovered and after 1 week solidified. The filtrate was extracted
1H NMR spectrum: da = 3.20, t, Jab = 6.64 Hz, 2H;
db = 2.43, t–t, J = 6.64, Jbg = 7.81, 2H; dg = 3.78, t–p,
j = 7.81, JBg = 8.20, 2H.
19F NMR spectrum: (AB4-type) dA = 85.3, nine lines, 1F;
dB = 69.0, JAB = 146.2 Hz (AB4-system).
Infrared spectrum (KBr): 2971, w–m; 2928, w; 2877, vw;
1447, m–s; 1429, m–s; 1362, w; 1309, w; 1288, m; 1231, s–vs;
1182, m; 1134, w; 1064, w; 1001, w–m; 969, w; 934, w–m; 871,

1194
R.W. Winter, G.L. Gard / Journal of Fluorine Chemistry 127 (2006) 1188–1194
[6] C.W. Tullock, D.D. Coffman, E.L. Muetterties, J. Am. Chem. Soc. 86
(1964) 357.
vs; 762, m–s; 739, sh, w–m; 706, w; 687, w; 645, m–s; 630, s–
vs; 589, m–s; 569, m–s; 645, m; 511, w–m.
[7] G. Kleemann, K. Seppelt, Chem. Ber. 112 (1979) 1140.
[8] G. Kleemann, K. Seppelt, Angew. Chem. 90 (1978) 547.
[9] R.A. Bekker, B.L. Dyatkin, I.L. Knunyants, Izv. Akad. Nauk SSSR, Ser.
Khim. 12 (1970) 2738.
Mass spectrum (70 eV: ion (m/z), %, assignment):
Rt = 6.92 min, 296, 82%, M+; 169, 73, (M ꢀ I)+; 141, 14,
+
+
+
+
SF5CH2 ; 127, 29, SF5 , I+; 109, 8, SF4 ; 89, 1, SF3 ; 70, 8,
+
SF2 ; 61, 24, C2H5S+; 59, 10, C2H3S+; 51, 2, SF+; 41, 100,
[10] R.N. Haszeldine, F. Nyman, J. Chem. Soc. (1956) 2684.
[11] J.C. Hansen, P.M. Savu, United States 5,286,352 (1994),
SF5(CF2)4CO2Li;
+
C3H5 ; 39, 22, C3H3 .
+
High-resolution mass spectrum calcd. for 12C3H619F127I32S:
295.91557. Found: 295.91552.
P.G. Nixon, Ph.D. Thesis, Portland State University, 1999
(SF5(CH2)2CO2Li).
[12] In-house work done at Portland State University.
[13] J. Wessel, G. Kleemann, K. Seppelt, Chem. Ber. 116 (1983) 2399.
[14] P.G. Nixon, J. Renn, R.J. Terjeson, Y.S. Choi, R. Winter, G.L. Gard, J.
Fluorine Chem. 91 (1998) 13.
References
[1] W. Tyrra, D. Naumann, J. Fluorine Chem. 125 (2004) 823.
[2] R.E. Noftle, W.B. Fox, J. Fluorine Chem. 9 (1977) 219.
[15] R. Winter, G.L. Gard, J. Fluorine Chem. 102 (2000) 79.
[16] R. Winter, R.J. Terjeson, G.L. Gard, J. Fluorine Chem. 89 (1998)
105.
[3] F.W. Hoover, D.D. Coffman, J. Org. Chem. 29 (1964) 3567.
[4] J. Wessel, H. Hartl, K. Seppelt, Chem. Ber. 119 (1986) 453.
[5] R. Winter, R. Dodean, G.L. Gard, in: V.A. Soloshonok (Ed.), Fluorine
Containing Synthons, ACS Symposium Series #911, Oxford University
Press/American Chemical Society, Washington, DC, 2005, pp. 87–119.
[17] P.G. Nixon, J. Mohtasham, R. Winter, G.L. Gard, B. Twamley, J.M.
Shreeve, J. Fluorine Chem. 125 (2004) 553.
[18] C. Merrill, Ph.D. Thesis, University of Washington, 1962.