New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitro- and 1-chloro-2,6-dinitrobenzenes

Article abstract of DOI:10.1016/j.jfluchem.2004.03.008

New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitrobenzene and 1-chloro-2,6-dinitrobenzene were prepared from the corresponding bis(4-chloro-3-nitrophenyl)disulfide and bis(4-chloro-3,5-dinitrophenyl)disulfide, respectively. The SF₅ derivatives were obtained by fluorination of the disulfides with AgF₂ according to Sheppard's method, while perfluoroalkylation was carried out by means of thermolytic reactions with xenon(II) bis(perfluoroalkylcarboxylates). The introduction of fluorine-containing, electron-withdrawing substituents into the aromatic ring (in the presence of other deactivating groups) reinforces the activation of the halogen substituent towards nucleophilic attack. Several nucleophilic substitution reactions have been carried out with these compounds, and as a result, some N- and S-containing groups were introduced in the benzene ring. For example, the previously unknown SF₅, CF₃S, and C₂F₅S analogues of trifluralin (Treflan) were prepared and characterized. Additional synthetic possibilities for heterocyclic chemistry are presented on the basis of reactions of the new 1-chloro-2,6-dinitrobenzene derivatives with ethyl thioglycolate wherein fluorine-containing derivatives of benzothiazole N-oxide were obtained as the main products.

Full text of DOI:10.1016/j.jfluchem.2004.03.008

Journal of Fluorine Chemistry 125 (2004) 1305–1316
New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of
1-chloro-2-nitro- and 1-chloro-2,6-dinitrobenzenes
Alexey M. Sipyagina,b, Vyacheslav S. Enshovb, Sergei A. Kashtanovb, Colin P. Batemana,
Brian D. Mullena, Ying-Teck Tana, Joseph S. Thrashera,*
aDepartment of Chemistry, The University of Alabama, Tuscaloosa, AL 35487-0336, USA
bInstitute of Problems of Chemical Physics Russian Academy of Sciences, Chernogolovka 142432, Moscow Region, Russia
Received 3 March 2004; accepted 22 March 2004
Available online 20 July 2004
Abstract
New 4-pentafluorosulfanyl and 4-perfluoroalkylthio derivatives of 1-chloro-2-nitrobenzene and 1-chloro-2,6-dinitrobenzene were prepared
from the corresponding bis(4-chloro-3-nitrophenyl)disulfide and bis(4-chloro-3,5-dinitrophenyl)disulfide, respectively. The SF5 derivatives
were obtained by fluorination of the disulfides with AgF2 according to Sheppard’s method, while perfluoroalkylation was carried out by means
of thermolytic reactions with xenon(II) bis(perfluoroalkylcarboxylates). The introduction of fluorine-containing, electron-withdrawing
substituents into the aromatic ring (in the presence of other deactivating groups) reinforces the activation of the halogen substituent towards
nucleophilic attack. Several nucleophilic substitution reactions have been carried out with these compounds, and as a result, some N- and S-
containing groups were introduced in the benzene ring. For example, the previously unknown SF5, CF3S, and C2F5S analogues of trifluralin
(Treflan1) were prepared and characterized. Additional synthetic possibilities for heterocyclic chemistry are presented on the basis of
reactions of the new 1-chloro-2,6-dinitrobenzene derivatives with ethyl thioglycolate wherein fluorine-containing derivatives of benzothia-
zole N-oxide were obtained as the main products.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Pentafluorosulfanyl benzenes; Perfluoroalkylthio benzenes; Fluorination; Perfluoroalkylation; Heterocycles; Herbicides; Pesticides
1. Introduction
million with 24,000 metric tons being produced [7,8].
Surprisingly, even with the recent increased interest in
superlipophilic groups [9–13], the corresponding SF5,
CF3S, and C2F5S analogues of trifluralin have not been
reported yet.
It is well known that the replacement of a hydrogen atom
in an aromatic or heterocyclic system by a fluorine atom or a
perfluoroalkyl group may have a significant beneficial effect
on the physical and biological properties of such a molecule
[1,2]. Introduction of groups such as RFS (RF ¼ CF3, C2F5,
etc.) and SF5, which possess some of the highest lipophilic
indices known [3], can be expected to offer an even more
enhanced biological effect [4].
One of the primary areas of application for such com-
pounds is in the field of agricultural chemistry. For example,
trifluralin (Treflan1) or 2,6-dinitro-4-trifluoromethyl-N,N-
di-n-propylaniline has been in agricultural use since the
1960s primarily as a pre-emergence herbicide [5,6]. Based
on usage, trifluralin generally ranks in the top 10 agricultural
pesticides in terms of annual sales. For example, in 1998
worldwide sales of trifluralin were estimated at US$ 300
Thus far, all agriculturally useful SF5-benzenes have
been prepared from meta-nitro or the para-nitro SF5-ben-
zenes [11,14,15]. The variety of derivatives possible is thus
limited by the ability to synthesize different compounds
from these two precursors, something that is made more
difficult by having such a strong deactivating group on the
aromatic ring [16–18]. A better method to prepare more
highly substituted SF5-benzenes is to utilize aromatic dis-
ulfides that contain the desired degree of substitution and
then take them through the fluorination steps [19]. Another
approach would be to synthesize a disulfide that, once
fluorinated, contains a halogen that is activated towards
nucleophilic aromatic substitution (i.e., ortho or para to the
SF5 group) [20]. Ortho-substituted SF5-benzene derivatives
[13] are examples of this approach as are the derivatives
described herein.
* Corresponding author. Tel.: þ1-205-348-8434; fax: þ1-205-348-9104.
E-mail address: fluorine@bama.ua.edu (J.S. Thrasher).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.03.008

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Accordingly, we have been developing synthetic routes to
The 13C NMR spectrum of 2a contains six separate signals;
three of which are quintets: the first at d 151.9 ppm
new aromatic and heterocyclic compounds containing both
superlipophilic groups as well as active halogens. The latter
are suitable for replacement by different nucleophilic
reagents in order to provide numerous new and potentially
biologically active molecules. We wish to report herein the
SF5, CF3S, and C2F5S analogues of trifluralin as well as a
wide variety of 2,6-dinitroanilines and other derivatives
containing these superlipophilic groups. A preliminary
report of this work has appeared [20].
(2JCÀSF ¼ 21:0 Hz, attributable to the carbon directly
4
attached to the SF5 group C-4), the second at d
130.3 ppm (3JCÀSF ¼ 4:0 Hz, attributable to the carbon
4
atom ortho to the SF5 group and the nitro group, C-3),
and the third at d 123.9 ppm (3JCÀSF ¼ 4:0 Hz, attributable
4
to the other ortho carbon atom, C-5). The broad signal at d
147.3 ppm can be assigned to the C-2 carbon atom con-
nected to the NO2 group. The other two resonances, at d
132.5 and 131.0 ppm, can be assigned to C-6 and C-1,
respectively. Compound 2b gave the typical 19F NMR
signals of an AB4 pattern: a multiplet (asymmetrical nonet)
2. Results and discussion
for the axial fluorine atom at 77.43 ppm (JSFÀSF
150:8 Hz) and a doublet of multiplets for the four equatorial
¼
4
The preparation of the 4-pentafluorosulfanyl and 4-per-
fluoroalkylthio derivatives of 1-chloro-2-nitro- and 1-
chloro-2,6-dinitrobenzene originates from bis(4-chloro-3-
nitrophenyl) and bis(4-chloro-3,5-dinitrophenyl)disulfides
(1a,b), which were obtained from the corresponding sulfo-
nyl chloride by reduction with HBr/PhOH in acetic acid
[21]. The successful fluorination of disulfide (1a) was
carried out as shown in Scheme 1, and 1-chloro-2-nitro-4-
pentafluorosulfanylbenzene (2a) was isolated in 29% yield.
Two byproducts were present in the reaction mixture; the
first, 1-chloro-3-nitro-6-fluoro-4-pentafluorosulfanylben-
zene (3) results from aromatic ring fluorination of compound
2a, while the second, 4-chloro-3-nitrobenzenesulfonyl fluor-
ide (4) [22] is believed to result from the presence of metal
oxides in the AgF2 or on the reactor surface. Raising the
reaction temperature from 120 to 130 8C increases the yield
of target compound 2a (29%) but at expense of increasing
the amount of ring fluorination product 3 (4%). The one-step
synthesis of 2 from disulfide 1 represents a marked improve-
ment over its previous four-step synthesis from bis-4-nitro-
phenyl disulfide in at best 5% overall yield [15]. Compound
2b was isolated as a lightly yellow colored solid in a 43%
yield. The yield from the fluorination process is unusually
high (cf. [14]) as most of the aromatic ring is protected with
electron-withdrawing groups.
fluorine atoms at 62.22 ppm (JSF ÀSF ¼ 151:6 Hz). The 13
C
NMR spectrum contains four signals; two of which are
4
quintets: the first at 151.5 ppm (2JCÀSF ¼ 23:2 Hz, attribu-
4
table to the carbon atom directly bonded to the SF5 group)
and the second at 125.8 ppm (3JCÀSF ¼ 4:6 Hz, attributable
4
to the carbon atoms ortho to the SF5 group).
Recently, we have also developed a method for perfluor-
oalkylation of heterocyclic thiols and disulfides by means of
thermolytic reactions with xenon (II) bis(perfluoroalkylcar-
boxylates) [23]. By using disulfides 1a,b, the method was
successfully extended to this class of aromatic compounds.
A plausible mechanism for the general perfluoroalkylation
of compound 1 is shown in Scheme 2.
The pathway of the conversion may be represented as
follows. Perfluoroalkyl radicals formed by thermolysis of
xenon bis(perfluorocarboxylates) react by free radical dis-
placement of the RS fragment on one of the sulfur atom of
the aromatic disulfides 1a,b with the generation of perfluor-
oalkylsulfides and RSꢀ moiety, which then recombines with
RF radical to form the desired derivatives 2c–f.
The yield of compounds 2e,f can reach as high as 70%
when the molar ratio of reagents is: disulfide:perfluorocar-
bonic acid:XeF2 1:5:4. When lower stoichiometries of the
perfluorocarbonic acids and XeF2 were used, some of the
starting disulfide remains unreacted. The influence of the
solvent (e.g., trifluoroacetic acid, perfluoropropionic acid,
dichloromethane, and acetonitrile) on the yield of the pro-
ducts 2e,f was also studied. The best results were obtained
when the reaction was carried out in dichloromethane, prob-
ably due to the high solubility of the disulfide in this solvent.
All structures were confirmed by spectroscopic methods
and some also by elemental analyses (see Section 3). For
example, the 19F NMR spectrum of compound 2a reveals
two multiplets that belong to the resonances of the SF5 group
at 80.40 ppm (axial fluorine, asymmetrical nonet) and
2
63.19 ppm (equatorial fluorines, d of m, J ¼ 152:0 Hz).
Scheme 1.

A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
1307
Scheme 2.
Compounds 2c,d were obtained as yellowish oils in yields
of about 16–17%, while 2e,f were isolated as brownish or
yellow crystals in the range of 66–70% yield. 19F NMR
spectra of compounds 2c,e displays singlets at À42.52 and
À41.62 ppm that can be attributed to the fluorine atoms of
CF3S group. Likewise, two signals at À91.70 and
À82.88 ppm (for 2d) or À90.88 and À82.88 ppm (for 2f)
(confirm the presence of the C2F5S moiety). As expected,
five resonances appear in the 13C NMR spectra of com-
pounds 2c,e for the five different types of carbon atoms.
reduced into the corresponding diamino derivatives 12a,b in
the presence of Fe powder. The general reaction conditions
can be found in Section 3 and in Scheme 3.
Compounds 2b,d,f readily react with secondary amines at
room temperature to give excellent yields of analogs of the
famous trifluoromethyl-substituted 2,6-dinitroaniline herbi-
cides, e.g. trifluralin (Treflan1) (Scheme 4).
Both the chlorine and at least one of the nitro substituents
in 1-chloro-2,6-dinitro-4-trifluoromethyl benzene can act as
good leaving groups and reactions of this substituted ben-
zene with sulfur-containing nucleophiles (e.g., potassium
ethylxanthate) proceed by a two-step process with the
formation of thianthrene derivatives [24]. By analogy to
the results shown in [24], one would expect the formation of
thianthrenes 16a,b from 2b,e according to Route A in
Scheme 5. But instead, Route B was observed under the
same reaction conditions. First, the chlorine atom was
substituted with an ethyl xanthate group to give the inter-
mediates 15a,b, which after loss of a molecule of COS
(similar to decarboxylation) resulted in the formation of the
S-ethyl-derivatives 17a,b.
The possibility to explore the heterocyclic chemistry of
compounds 2b,e,f became available through their reactions
with ethyl thioglycolate [25]. These reactions proceeded
through the intermediate formation of the thioglycolate
derivatives 18a–c (not isolated), followed by an intramole-
cular ring closure involving one of the nitro groups in
presence of base (NEt3), thereby giving the benzothia-
1
Quartets with a large JCÀF coupling constant of about
310 Hz are due to the CF3 groups, while the other two
quartets: at 128.0 (3JCÀSCF ¼ 2:5 Hz), 132.6 (4JCÀSCF
¼
3
3
1:0 Hz) (for 2c) and at 126.6 ppm (3JCÀSCF ¼ 2:7 Hz),
3
134.2 ppm (4JCÀSCF ¼ 1:1 Hz) (for 2e) are due to the ipso
3
carbon atom (connected directly to CF3S group) and the
carbon atoms ortho to that carbon atom, respectively.
The reactivity of compound 2a with a variety of different
nucleophiles revealed the susceptibility of the chlorine atom
to nucleophilic aromatic substitution. The coupling reaction
of 2a in the presence of copper–bronze was also carried out.
As a result, the biphenyl derivative 11a was obtained as
shown in Scheme 3. This coupling reaction was carried out
in the presence of the ring fluorinated derivative 3, and the
asymmetric biphenyl 11b was found to be in the reaction
mixture. A small amount of 1-nitro-3-pentafluorosulfanyl-
benzene was also detected, which is a product of dechlor-
ination of starting material 2a. Dinitrobiphenyls 11a,b were

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A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
Scheme 3.
zole-N-oxides 19a–c. The transformation of benzothiazole-
N-oxide 19b into the hydroxamic acid 20 in the presence of
hydroxylamine displays the reactivity of these heterocyclic
compounds (Scheme 6).
trifluralin [27]. High-resolution mass spectra (HRMS) were
recorded on a VG Instruments Autospec mass spectrometer,
where the uncertainty in the mass measurements was
Æ0.002 Da. Proof-of-purity was indicated by a single peak
in the GC chromatogram, the absence of extra signals in the
multinuclear NMR spectra, and an exact mass determina-
tion.
3. Experimental
Melting points were determined in open capillaries and
are uncorrected. Column chromatography was performed on
silica gel 60, 230–400 mesh (Merck), with the solvents
indicated. TLC was run on silica gel 60 F254 plates (Merck).
1H, 13C, and 19F NMR spectra were recorded on either a
Bruker AM 360 or 500 spectrometer, using Me4Si and
CFCl3 as internal standards, respectively, and CDCl3 or
Me2SO-d6 as solvent unless otherwise stated. Chemical
shifts are reported in ppm; second-order spectra, especially
the typical AB4 spin-patterns observed for SF5 groups, were
simulated with the aid of our PC version of LAOCN3 [26].
Infrared spectra were recorded on a BioRad FTS-40 FT-IR
spectrometer; frequencies are reported in cmÀ1. GC–MS
analyses were carried out on a Hewlett-Packard (HP) 5890
gas chromatograph-spectrometer (70 eV) using a 30 m
capillary column. The assignment of the mass-spectral
fragments for compounds 13a–h and 14a–d was aided by
the previous work of Mallen and co-workers on benefin and
3.1. Preparation of disulfides 1a,b
3.1.1. Bis(4-chloro-3-nitrophenyl)disulfide (1a)
The starting disulfide was obtained by reduction of the
commercially available 4-chloro-3-nitrobenzenesulfonyl
chloride (Aldrich) with an HBr solution in glacial acetic
acid in presence of phenol [21]. The disulfide 1a was
obtained in 85% yield overall as yellow crystals, mp
115 8C (lit. 116–117 8C [21]).
3.1.2. Bis(4-chloro-3,5-dinitrophenyl)disulfide (1b)
This starting aromatic disulfide was obtained in a three-
step synthesis. First, the potassium salt of 4-chloro-3,5-
dinitrobenzene sulfonic acid was obtained from chloroben-
zene [28]. Second, this salt was transformed into the corre-
sponding sulfonyl chloride according to Ullmann’s
procedure [29]. Third, 20 g (0.066 mol) of the sulfonyl
chloride was gradually dissolved in 340 mL of glacial acetic

A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
1309
acid saturated with 35 g of gaseous HBr. Phenol (6.9 g) was
added to the reaction mixture, which was first heated care-
fully under stirring to 55–60 8C (exothermic reaction), and
then to 65–70 8C. The reaction mixture was kept at 60 8C
with stirring for ca. 26 h. The solid that precipitated was
collected by filtration after cooling the reaction mixture;
washed with glacial acetic acid, ethanol, and hexane; and
then dried. Yield is 14 g (90%). The precipitate was recrys-
tallized from glacial acetic acid to give a yellow solid
1
(13.3 g, mp 188–189 8C). H NMR (CDCl3): d 8.09 (s);
IR (Nujol): 3063 (C–H), 1536, 1351, 1278, 1129, 1054, 914,
883, 722 cþmÀ1; MS m/z (rel. int.): 466 [M]þ (73), 234
½M=2 þ HŠ
(100),
233
[M/2]þ
(23),
218
[(M=2 þ H)ÀO]þ (8), 188 [M=2 þ HÀNO2]þ (31); HRMS
calcd. for C12H4Cl2N4O8S2, 465.885, found 465.883.
3.2. Fluorination of disulfides (general method)
The reaction with AgF2 was performed in a stainless steel
reactor that had previously been passivated with elemental
fluorine. While being passivated, the reactor contained six
copper sheets (10 mm  100 mm  0:2 mm) that would
later be used in the reactions. The reactor was charged with
0.033 mol of disulfide 1a,b, 195 g of AgF2, and the copper
strips, with all manipulations being carried out within a dry
box. The vessel was then closed, evacuated on a vacuum
line, cooled to 0 8C, and 125 mL of CFC 113 was transferred
in. After warming to room temperature, the vessel was held
at 60 8C for 2 h and then at 125–130 8C for 3 h (for 2a) or at
130–135 8C for 4 h (for 2b), under intermittent shaking. The
reactor was then cooled to room temperature, and the
reaction mixture was extracted three times with chloroform.
The extract was filtered, washed with a 10% aqueous
NaHCO3 solution, and dried over Na2SO4. After removal
of the chloroform, the resulting oil was separated by column
chromatography (silica, hexane:benzene 4:1 (for 2a) or
hexane:benzene 3:1 (for 2b)).
Scheme 4.
Scheme 5.

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A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
Scheme 6.
3.2.1. 1-Chloro-2-nitro-4-pentafluorosulfanylbenzene
(2a)
8.52 (1H, d, J ¼ 2:0 Hz). 19F NMR: d 64.61 (s). MS m/z (rel.
int.): 239 [M]þ (100), 209 [M À NO]þ (35), 126
[209 À SO2F]þ (66). HRMS calcd. for C6H3ClFNO4S
238.946, found 238.944.
1
Yield 29%, yellow oil, n2D5 ¼ 1:4834. H NMR (CDCl3)
[15]: d 7.71 (1H, d, J ¼ 8:8 Hz, Ar), 7.92 (1H, dd, J ¼ 8:8,
2.5 Hz, Ar), 8.30 (1H, d, J ¼ 2:5 Hz, Ar). 19F NMR: d 63.19
2
(d of m, 4F, JSF ÀSF ¼ 152:0 Hz, SF4), 80.40 (m, 1F,
3.2.4. 1-Chloro-2,6-dinitro-4-pentafluorosulfanylbenzene
(2b)
4
2JSFÀSF ¼ 152:0 Hz, SF). 13C NMR:
d 123.9 (qu,
4
3JCÀSF ¼ 4:0 Hz, C-3), 130.3 (qu, JCÀSF ¼ 4:0 Hz, C-
Yield 9.35 g (43%) as slightly yellow solid, mp 85–87 8C.
3
4
4
5), 131.0 (s, C-1), 132.5 (s, C-6), 147.3 (broad s, C-2),
2
1H NMR (CDCl3): d 8.40 (s, Ar); 19F NMR: d 63.18 (d of m,
151.9 (qu, JCÀSF ¼ 21:0 Hz, C-4). IR (neat): 3110 (aro-
4F,
JSF ÀSF ¼ 152:8 Hz,
SF4),
77.42
(m,
1F,
4
4
matic C–H stretch), 1596, 1551, 1499 (asymmetric N–O
stretch), 1359 (symmetric N–O stretch), 909, 853, 832 cmÀ1
(aromatic C–N stretch). MS m/z (rel. int.): 283 [M]þ (91),
264 [M À F]þ (28), 129 [M À NO2–SF4]þ (100). HRMS
calcd. for C6H3ClF5NO2S 282.949 (for 35Cl) and 284.946
(for 37Cl), found 282.949 and 284.945, respectively.
JSFÀSF ¼ 152:8 Hz, SF); 13C NMR: d 124.6 (s, C-1),
4
3
125.8 (qu, JCÀSF ¼ 4:6 Hz, C-3, C-5), 149.3 (s, C-2, C-
4
2
6), 151.5 (qu, JCÀSF ¼ 23:4 Hz, C-4). MS m/z (rel. int.):
4
328 [M]þ (47), 309 [M À F]þ (11), 247 [M À NO2–Cl]þ
(11), 236 [M À 2NO2]þ (10), 217 [309À2NO2]þ (11), 201
[247ÀNO2]þ, [M À SF5]þ (7), 109 [M À SF5–2NO2]þ
(100). HRMS calcd. for C6H2ClF5N2O4S 327.934, found
327.934.
3.2.2. 1-Chloro-2-fluoro-6-nitro-4-
pentafluorosulfanylbenzene (3)
Yield 4%, yellow oil, n2D5 ¼ 1:4682. 1H NMR (CDCl3): d
7.83 (1H, dd, J ¼ 8:1, 2.5 Hz, Ar), 8.14 (1H, m, Ar). 19F
NMR: d À106.93 (s, 1F, F–Ar), 60.78 (d of m, 4F,
3.3. Perfluoroalkylation of bis(4-chloro-3,5-
dinitrobenzene) disulfide (1)—general method
2JSF ÀSF ¼ 152:0 Hz,
SF4),
76.76
(m,
1F,
Disulfide 1a,b (8.57 mmol) was added under stirring at
À30 8C to a mixture of XeF2 and the corresponding per-
fluorocarbonic acid in 30 mL of CH2Cl2 (the molecular ratio
of disulfide:XeF2:perfluorocarbonic acid was 1:3–4:5–6).
The reaction mixture was stirred while gradually being
allowed to warm to room temperature. The end of gas
evolution determined the end of the reaction. The reaction
mixture was then washed with a saturated solution of
NaHCO3 and dried on Na2SO4. After removal of solvent,
the remaining residue was separated via column chromato-
graphy (silica, hexane:benzene 1:2).
4
2JSFÀSF ¼ 152:0 Hz, SF). 13C NMR:
d 118.4 (m,
4
2JCÀF ¼ 26:6, 3JCÀSF ¼ 4:0 Hz, C-3), 119.1 (qu,
4
2
3JCÀSF ¼ 4:0 Hz, C-5), 120.5 (d, JCÀF ¼ 21:4 Hz, C-1),
4
148.2 (broad s, C-6), 151.5 (m, C-4), 158.2 (d,
JCÀF ¼ 257:5 Hz, C-2). IR (neat): 3113 (aromatic C–H
stretch), 1556, 1467, 1431 (asymmetric N–O stretch),
1364 (symmetric N–O stretch), 907, 862, 813 cmÀ1 (aro-
matic C–N stretch). MS m/z (rel. int.): 301 [M]þ (100), 282
[M À F]þ (23). HRMS calcd. for C6H2ClF6NO2S 300.940,
found 300.939.
3.2.3. 4-Chloro-3-nitrobenzenesulfonyl fluoride (4)
1
3.3.1. 1-Chloro-2-nitro-4-trifluoromethylthiobenzene (2c)
Yield 16.2%, yellow oil. 1H NMR (CDCl3): d 7.64 (1H, d,
J ¼ 8:4 Hz, Ar), 7.80 (1H, dd, J ¼ 2:1, 8.1 Hz, Ar), 8.16
mp 56–58 8C (lit. 58–60 8C [22]). H NMR (CDCl3): d
7.90 (1H, d, J ¼ 8:5 Hz), 8.16 (1H, dd, J ¼ 8:5, 2.0 Hz),

A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
1311
(1H, d, J ¼ 2:1 Hz, Ar); 19F NMR: d À42.52 (s, CF3); 13C
residue was washed with water and dissolved in benzene.
The benzene layer was dried over sodium sulfate and then
evaporated in vacuum. The residue was washed with hexane
and then recrystallized from hexane to yellow-white solid
that weighed 0.20 g, a 68% overall yield, mp 65–66 8C. 1H
NMR (CDCl3): 1.51 (3H, t, J ¼ 7:0 Hz, CH3), 4.26 (2H,
quartet, J ¼ 7:0 Hz, CH2), 7.12 (1H, d, J ¼ 9:0 Hz, Ar),
7.90 (1H, dd, J ¼ 9:0, 2.8 Hz, Ar), 8.25 (1H, d, J ¼ 2:8 Hz,
NMR: d 128.0 (q, 3JCÀSCF ¼ 2:5 Hz, C-4), 128.8 (q, JCF
¼
3
3
309:1 Hz, CF3), 130.4 (s, C-1), 132.6 (q, 4JCÀSCF ¼ 1:0 Hz,
3
C-5), 133.0 (s, C-6), 140.2 (q, 4JCÀSCF ¼ 0:9 Hz, C-3), 148.1
3
(broad s, C-2). MS m/z (rel. int.): 257 [M]þ (100), 238
[M À F]þ (4), 211 [M À NO2]þ (10), 188 [M À CF3]þ (7),
142 [211ÀCF3]þ (53), 107 [142ÀCl]þ (23), 69 [CF3]þ
(32). HRMS calcd. for C7H3ClF3NO2S, 256.952, found
256.953.
2
Ar); 19F NMR: d 61.74 (d of m, 4F, JSF ÀSF ¼ 152:0 Hz,
4
SF4), 80.54 (m, 1F, 2JSFÀSF ¼ 152:0 Hz, SF); 13C NMR: d
4
3.3.2. 1-Chloro-2-nitro-4-pentafluoroethylthiobenzene (2d)
Yield 16.9%, yellow oil. 1H NMR (CDCl3): d 7.66 (1H, d,
J ¼ 8:4 Hz, Ar), 7.81 (1H, dd, J ¼ 2:1, 8.1 Hz, Ar), 8.17
(1H, d, J ¼ 2:1 Hz, Ar); 19F NMR: d À91.70 (2F, s, CF2–
CF3), À82.88 (3F, s, CF2–CF3); 13C NMR: d 118.4 (qt,
14.0 (s, CH3), 66.3 (s, CH2), 113.9 (s, C-6), 124.1 (qu,
3JCÀSF ¼ 4:9 Hz, C-3), 131.4 (C-5, qu, 3JCÀSF ¼ 4:9 Hz),
4
4
2
138.6 (s, C-2), 144.9 (qu, JCÀSF ¼ 20:0 Hz, C-4), 154.1
4
(C-1). IR (Nujol): 3126, 3097 (aromatic C–H stretch), 1618,
1587, 1533 (asymmetric N–O stretch), 1361 (symmetric N–
O stretch), 913, 878, 865, 840 cmÀ1 (aromatic C–N stretch).
MS m/z (rel. int.): 293 [M]þ (35), 274 [M À F]þ (25), 265
[M À C2H4]þ (100), 249 [M À C2H4O]þ (40), 235
[265ÀNO]þ (13), 127 [SF5]þ (33). HRMS calcd. for
C8H8F5NO3S 293.015, found 293.014.
2
JCF ¼ 286:6 Hz, JCÀCF ¼ 36:2 Hz, CF2–CF3), 119.7 (tq,
3
2JCÀCF ¼ 41:1 Hz, JCF ¼ 290:9 Hz, CF2–CF3), 123.3 (t,
3
3JCÀSCF ¼ 3:0 Hz, C-4), 130.7 (s, C-1), 132.9 (s, C-6),
3
133.4 (s, C-5), 141.0 (s, C-3), 148.1 (m, C-2). MS m/z
(rel. int.): 307 [M]þ (100), 271 [M À Cl]þ (1), 188
[M À C2F5]þ (18), 142 [188ÀNO2]þ (60), 119 [C2F5]þ
(8), 107 [142ÀCl]þ (26), 75 [M À SC2F5–NO2–Cl]þ (11),
69 [CF3]þ (27). HRMS calcd. for C8H3ClF5NO2S, 306.949,
found 306.949.
3.4.2. Preparation of 1-methylthio-2-nitro-5-
pentafluorosulfanylbenzene (6)
Into a solution of 0.284 g (1.0 mmol) of compound 2a and
5 mL of ethanol was added 0.10 g (1.4 mmol) of sodium
thiomethoxide. The solution was maintained at room tem-
perature for 3 h and then the solvent was removed under
vacuum. The dried residue was washed with water and solid
was extracted with benzene. The benzene extract was dried
over sodium sulfate. The resulting residue was washed with
hexane and then recrystallized from hexane. The product
was obtained as a yellow solid (0.24 g) in an 81% yield, mp
3.3.3. 1-Chloro-2,6-dinitro-4-trifluoromethylthiobenzene
(2e)
1
Yield 70%, brownish crystals, mp 35–37 8C. H NMR
(CDCl3): d 8.27 (s, Ar); 19F NMR: d À41.62 (s, CF3); 13C
3
NMR: d 123.6 (C-1), 126.6 (q, JCÀSCF ¼ 2:7 Hz, C-4),
3
128.3
(q,
1JCÀF ¼ 310:1 Hz,
CF3),
134.2
(q,
4JCÀSCF ¼ 1:1 Hz, C-3, C-5), 149.8 (s, C-2, C-6). MS m/
3
z (rel. int.): 302 [M]þ (100), 283 [M À F]þ (5), 256
[M À NO2]þ (2), 233 [M À CF3]þ (2), 210 [M À 2NO2]þ
(9), 141 [210ÀCF3]þ (16), 69 [CF3]þ (19). HRMS calcd. for
C7H2ClF3N2O4S, 301.938, found 301.937.
107–108 8C. H NMR (CDCl3): d 2.56 (3H, s, MeS), 7.47
1
(1H, d, J ¼ 8:9 Hz, Ar), 7.93 (1H, dd, J ¼ 8:9, 2.3 Hz, Ar),
8.67 (1H, d, J ¼ 2:3 Hz, Ar); 19F NMR: d 63.46 (d of m, 4F,
d,
2JSF ÀSF ¼ 152:0 Hz,
SF4),
82.01
(m,
1F,
4
2JSFÀSF ¼ 152:0 Hz, SF); 13C NMR: d 16.0 (s, CH3),
4
3
3.3.4. 1-Chloro-2,6-dinitro-4-pentafluoroethylthiobenzene
(2f)
124.2 (qu, JCÀSF ¼ 4:6 Hz, C-3), 125.8 (s, C-6), 130.2
4
(broad s, C-5), 144.2 (broad s, C-2), 144.4 (s, C-1), 149.0
Yield 66%, yellow crystals, mp 65–67 8C. 1H NMR
(CDCl3): d 8.27 (s, Ar); 19F NMR: d À90.88 (q, 2F,
JFÀF ¼ 3:3 Hz, CF2CF3), À82.74 (t, 3F, JFÀF ¼ 3:3 Hz,
CF2CF3). MS m/z (rel. int.): 352 [M]þ (100), 283
[M À CF3]þ (6), 237 [283ÀNO2]þ (2), 233 [M À C2F5]þ
(4), 191 [237ÀNO2]þ (2), 187 [233ÀNO2]þ (1), 106
[187ÀNO2–Cl]þ (20). HRMS calcd. for C8H2ClF5N2O4S,
351.934, found 351.934.
(qu, 2JCÀSF ¼ 20:0 Hz, C-4). IR (Nujol): 3113 (aromatic C–
4
H stretch), 1600, 1560, 1520 (asymmetric N–O stretch),
1342 (symmetric N–O stretch), 902, 849 cmÀ1 (aromatic C–
N stretch). MS m/z (rel. int.): 295 [M]þ (100), 280
[M À CH3]þ (7), 276 [M À F]þ (24), 265 [M À NO]þ
(63), 264 [M À CH3S]þ (13), 250 [280ÀNO]þ (14), 234
[280ÀNO2]þ (7). HRMS calcd. for C7H6F5NO2S2 294.976,
found 294.975.
3.4. Reactions of compound 2a with nucleophiles
3.4.3. Preparation of 2-nitro-4-pentafluorsulfanyl-1-
piperidinobenzene (7)
3.4.1. Preparation of 1-ethoxy-2-nitro-4-
pentafluorosulfanylbenzene (5)
To solution of 0.06 g (1.0 mmol) of KOH in 5 mL of
absolute ethanol was added 0.284 g (1.0 mmol) of com-
pound 2a. The mixture was maintained at room temperature
for 3 h and then the ethanol was removed under vacuum. The
To a solution of 0.284 g (1.00 mmol) of compound 2a and
5 mL of ethanol was added 0.15 mL of piperidine. The
reaction was maintained at room temperature for 3 h and then
refluxed for 20 min. The solvent was then removed under
vacuum and the resulting dry residue was washed with water.
The residue was then extracted with benzene and dried with

1312
A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
sodium sulfate. The benzene was evacuated and residue was
purified by column chromatography on silica gel, which was
eluted with a mixture of hexane:benzene 1.5:1. The residue
from the column was crystallized from hexane to yield 0.23 g
(69%) of orange-red solid, mp 80–81 8C. 1H NMR (CDCl3): d
1.68 (2H, m, piperidine), 1.72 (4H, t, J ¼ 5:4 Hz, piperidine),
3.14 (4H, t, J ¼ 5:4 Hz, piperidine), 7.06 (1H, d, J ¼ 9:2 Hz,
Ar), 7.73 (1H, dd, J ¼ 9:2, 2.3 Hz, Ar), 8.18 (1H, d,
temperature for next 1 h. The reaction mixture was extracted
3–4 times with hot chloroform, and the chloroform solutions
were filtered. The solvent was evacuated in vacuum and the
remaining residue was separated on a column packed with
silica (eluant benzene:hexane 1:2). The first separated com-
pound was 0.4 g of recovered starting material 2, the sec-
ond—0.15 g of dechlorination process product 1-nitro-3-
pentafluorosulfanylbenzene,
biphenyl 11b, and fourth—0.95 g of biphenyl 11a. Two last
the
third—asymmetrical
J ¼ 2:3 Hz, Ar); 19F NMR: d 61.86 (d of m, 4F,
2
2JSF ÀSF ¼ 151:7 Hz, SF4), 81.85 (m, 1F, JSFÀSF
¼
compounds were recrystallized from hexane.
4
4
151:7 Hz, SF); 13C NMR: d 23.7 (s), 25.5 (s), 51.9 (s),
119.4 (C-6), 125.3 (qu, JCÀSF ¼ 4:6 Hz, C-3), 130.5 (qu,
3.5.1. 2,20-Dinitro-4,40-bis-pentafluorosulfanylbiphenyl
(11a)
3
4
3JCÀSF ¼ 4:7 Hz, C-5), 138.3 (broad s, C-2), 143.4 (qu,
4
1
2JCÀSF ¼ 21:8 Hz, C-4), 148.0 (s, C-1). IR (Nujol): 3122
Yield 34%, mp 199–200 8C. H NMR (CDCl3): d 7.46
4
(aromatic C–H stretch), 1610, 1563, 1522 (asymmetric N–O
stretch), 1302 (symmetric N–O stretch), 888, 845 cmÀ1 (aro-
matic C–N stretch). MS m/z (rel. int.): 332 [M]þ (25), 315
[M À OH]þ (100), 297 [315 À H2O]þ (20), 285
[315 À NO]þ (61), 270 [297 À HCN]þ (37), 256
[297 À CH2CN]þ (35), 245 [315 À C4H8N]þ (23), 230
[315 À C5H11N]þ (37). HRMS calcd. for C11H13F5N2O2S
332.062, found 332.062.
(1H, d, J ¼ 8:4 Hz, Ar), 8.53 (1H, dd, J ¼ 8:4, 2.1 Hz, Ar),
8.70 (1H, d, J ¼ 2:1 Hz, Ar); 19F NMR: d 62.93 (d of m, 4F,
2
2JSF ÀSF ¼ 152:0 Hz, SF4), 80.27 (m, 1F, JSFÀSF
¼
4
4
152:0 Hz, SF); 13C NMR: d 123.4 (qu, JCÀSF ¼ 4:2 Hz,
3
4
C-3, C-30), 131.0 (qu, 3JCÀSF ¼ 4:6 Hz, C-5, C-50), 131.1 (s,
4
C-6, C-60), 136.0 (s, C-1, C-10), 146.3 (broad s, C-2, C-20),
154.0 (qu, JCÀSF ¼ 20:8 Hz, C-4, C-40). IR (Nujol): 1539
2
4
(asymmetric N–O stretch), 907, 876, 842 cmÀ1 (S–F). MS
m/z (rel. int.): 496 [M]þ (1), 495 [M À H]þ (1), 477
[M À F]þ (26), 450 [M À NO2]þ (100), 434 [450ÀO]þ
(18), 420 [450ÀNO]þ (11).
3.4.4. Preparation of 2-nitro-4-pentafluorosulfanylaniline
(9)
A solution containing 5.20 g (0.18 mol) of compound 2a
and 10 mL of 27% ammonia was sealed in an ampoule and
heated to 130–135 8C for 4 h. The solid product was filtered,
washed with water, and dried in air. The residue was purified
by column chromatography on silica gel, which was eluted
with benzene. Unreacted starting material (2a, 1.30 g) and
an orange solid (9, 2.60 g, 72%) were collected, mp 137–
138 8C. 1H NMR (CDCl3): d 6.42 (2H, broad s, NH2), 6.86
(1H, d, J ¼ 9:2 Hz, Ar), 7.70 (1H, dd, J ¼ 9:2, 2.5 Hz, Ar),
8.57 (1H, d, J ¼ 2:5 Hz, Ar); 19F NMR: d 63.53 (d of m, 4F,
3.5.2. 2,20-Dinitro-6-fluoro-4,40-bis-
pentafluorosulfanylbiphenyl (11b)
mp 151–152 8C. 1H NMR (CDCl3): d 6.18 (1H, dd,
J ¼ 8:6, 1.8 Hz, Ar), 7.46 (1H, d, J ¼ 8:6 Hz, Ar), 8.16
(1H, d, J ¼ 9:3 Hz, Ar), 8.51 (1H, s, Ar), 8.77 (1H, d,
J ¼ 1:8 Hz, Ar); 19F NMR: d À106.93 (1F, s, Ar–F),
2
60.40 (d of m, 4F, JSF ÀSF ¼ 152:0 Hz, SF4), 60.72 (d of
4
2
m, 4F, JSF ÀSF ¼ 152:0 Hz, SF4), 76.62 (m, 1F,
4
2JSFÀSF ¼ 152:0 Hz, SF), 77.63 (m, 1F, JSFÀSF
¼
2
4
4
2JSF ÀSF ¼ 149:0 Hz,
SF4),
83.81
(m,
1F,
152:0 Hz, SF); 13C NMR: d 119.1 (s, C-3, C-30), 119.5
4
3
2JSFÀSF ¼ 149:0 Hz, SF); 13C NMR: d 118.4 (s, C-6),
(m, C-5), 123.8 (qu, JCÀSF ¼ 4:0 Hz, C-50), 125.1 (d,
4
4
125.2 (qu, 3JCÀSF ¼ 4:8 Hz, C-3), 130.1 (qu,
2JCÀF ¼ 20:8 Hz, C-1), 129.0 (s, C-10), 131.3 (s, C-60),
4
2
3JCÀSF ¼ 4:8 Hz, C-5), 132.3 (s, C-2), 142.3 (qu,
146.8 (s, C-20), 147.0 (s, C-2), 154.4 (qu, JCÀSF
¼
4
4
2JCÀSF ¼ 20:0 Hz, C-4), 145.9 (s, C-1). IR (neat): 3481,
21:3 Hz, C-4, C-40), 158.3 (d, JCÀF ¼ 257:6 Hz, C-6). IR
(Nujol): 1575 (asymmetric N–O stretch), 921, 897, 862,
837 cmÀ1 (S–F). MS m/z (rel. int.): 495 [M À F]þ (1), 468
[M À NO2]þ (100), 452 [468ÀO]þ (17), 438 [468ÀNO]þ
(15), 360 [468ÀSF4]þ (44).
4
3349 (aromatic N–H stretch asymmetric, symmetric), 1632,
1571, 1515 (asymmetric N–O stretch), 835 cmÀ1 (aromatic
C–N stretch). MS m/z (rel. int.): 264 [M]þ (100), 248
[M À NH2]þ (7), 245 [M À F]þ (9), 218 [M À NO2]þ
(28). HRMS calcd. for C6H5F5N2O2S 263.999, found
263.998.
3.6. Reductions of nitrocompounds were carried out
with Fe powder by refluxing in ethanol in presence of
hydrochloric acid according to general method
described in [13]
3.5. Coupling reaction of 1-chloro-2-nitro-4-
pentafluorosulfanylbenzene (2a)
A mixture of 3.60 g (0.0127 mol) of compound 2a (con-
taining a several percent of fluorinated derivative 4) and 3 g
of sea sand was heated under stirring in a flask to 210 8C and
2 g of Cu–bronze powder was added gradually in a tem-
perature range 220–225 8C. After 0.5 h the reaction mixture
had transformed into a solid, and the solid mass kept at this
3.6.1. 2-Chloro-5-pentafluorosulfanylaniline (8)
Purified by column chromatography on silica gel, eluted
with hexane:benzene 1:1. Yield 83% of yellowish oil,
n2D4 ¼ 1:4965. 1H NMR (CDCl3): d 4.25 (2H, broad s,
NH2), 7.04 (1H, dd, J ¼ 8:8, 2.8 Hz, Ar), 7.13 (1H, d,
J ¼ 2:8 Hz, Ar), 7.29 (1H, d, J ¼ 8:8, Ar); 19F NMR: d

A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
1313
2
60.57 (d of m, 4F, 2JSF ÀSF ¼ 151:0 Hz, SF4), 82.11 (m, 1F,
2JSFÀSF ¼ 150:0 Hz, SF), 84.28 (m, 1F, JSFÀSF
¼
4
4
4
2JSFÀSF ¼ 151:0 Hz, SF); 13C NMR: d 112.9 (C-6), 116.0
150:0 Hz, SF); 13C NMR: d 103.5 (d, JCÀSF ¼ 4:0 Hz,
3
4
4
3
(qu, JCÀSF ¼ 4:8 Hz C-4), 121.9 (s, C-2), 129.2 (s, C-3),
C-3), 108.5 (s, C-30), 112.5 (d, 2JCÀF ¼ 20:0 Hz, C-1), 113.3
4
3
3
143.0 (C-1), 153.0 (qu, J ¼ 18:0 Hz, C-5). IR (neat): 3505,
3408 (aromatic N–H stretch asymmetric, symmetric), 1632
(N–H bend), 1313 (symmetric N–O stretch), 846, 813 cmÀ1
(aromatic C–N stretch). MS m/z (rel. int.): 253 [M]þ (100),
145 [M À SF4]þ (100), 126 ½M À SF5]þ (45). HRMS calcd.
for C6H5ClF5NS 252.975, found 252.975.
(qu, JCÀSF ¼ 4:0 Hz, C-5), 116.0 (qu, JCÀSF ¼ 4:0 Hz,
4
4
C-50), 118.3 (s, C-10), 131.5 (s, C-60), 144.8 (s, C-20), 146.0
(d, 3JCÀF ¼ 5:0 Hz, C-2), 154.9 (qu, 2JCÀSF ¼ 17:8 Hz, C-
4
40), 155.3 (qu, JCÀSF ¼ 17:4 Hz, C-4), 159.7 (d,
2
4
JCÀF ¼ 247:1 Hz, C-6). IR (Nujol): 3482, 3431, 3333,
3223 (NH), 917, 841, 810, 791 cmÀ1 (S–F). MS m/z (rel.
int.): 454 [M]þ (100), 434 [M À HF]þ (33), 327 [M À SF5]þ
(41). HRMS calcd. for C12H9F11N2S2 454.003, found
436.004. Anal. calcd.: C, 31.72; H, 2.00; N, 6.17; S,
14.12. Found: C, 32.13; H, 1.91; N, 6.09; S, 14.52.
3.6.2. 4-Pentafluorosulfanyl-1,2-phenylenediamine (10)
Purified by column chromatography on silica gel, eluted
with benzene. Yield 87% of slight-yellow crystals, mp 70–
1
71 8C. H NMR (CDCl3): d 3.47 (4H, broad s, NH2), 6.64
(1H, d, J ¼ 8:5 Hz, Ar), 7.10 (1H, dd, J ¼ 8:5, 2.6 Hz, Ar),
3.7. Reactions of secondary amines with 1-chloro-2,6-
dinitrobenzene derivatives (2b,c)—general method for
the preparation of 13a–h and 14a–d
7.12 (1H, d, J ¼ 2:6 Hz, Ar); 19F NMR: d 65.33 (d of m, 4F,
2
2JSF ÀSF ¼ 148:0 Hz, SF4), 88.51 (m, 1F, JSFÀSF
¼
4
4
148:0 Hz, SF); 13C NMR: d 114.3 (s, C-6), 114.4 (qu,
3JCÀSF ¼ 4:8 Hz, C-3), 118.5 (qu, JCÀSF ¼ 4:8 Hz, C-
To a solution of 1.5 mmol of 1-chloro-2,6-dinitrobenzene
derivative 2b,c in 10 mL of methanol (or ethanol) was added
under stirring 2.5 equivalents of amine. After 30 min the
solvent was removed under vacuum. The resulting residue
was washed with water and extracted with benzene or
chloroform. After drying over Na2SO4, the product was
purified by column chromatography [silica, hexane:benzene
4:1 (dialkylamino derivatives)] or recrystallized from aqu-
eous ethanol (or heptane for the piperazine derivatives).
3
4
4
2
5), 133.2 (s, C-2), 138.1 (s, C-1), 145.6 (qu, JCÀSF
¼
4
17 Hz, C-4). IR (neat): 3489, 3445, 3400, 3370, 3328
(aromatic N–H stretch asymmetric, symmetric), 1625 (N–
H bend), 1080 (C–N stretch), 846 cmÀ1 (aromatic C–N
stretch). MS m/z (rel. int.): 234 [M]þ (100), 126
[M À SF4]þ (50), 107 [M À SF5]þ (50). HRMS calcd. for
C6H7F5N2S 234.025, found 234.023.
3.6.3. 2,20-Diamino-4,40-bis-pentafluorosulfanylbiphenyl
(12a)
3.7.1. 2,6-Dinitro-4-pentafluorosulfanyl-N,N-di-n-
propylaniline (13a)
Purified by column chromatography on silica gel, eluted
with hexane:benzene 1:2. Yield 86% as slight-yellow solid,
mp 191–192 8C (methanol). 1H NMR (CDCl3): d 3.87 (2H,
broad s, NH2), 7.16 (1H, d, J ¼ 8:4 Hz, Ar), 7.19 (1H, d,
J ¼ 2:0 Hz, Ar), 7.22 (1H, dd, J ¼ 8:4, 2.0 Hz, Ar); 19F
Yield 84% as an orange-red solid, mp 66–67 8C. 1H NMR
(CDCl3): d 0.88 (6H, t, J ¼ 7:3 Hz, CH3), 1.62 (4H, m,
J ¼ 7:3 Hz, CH2), 2.97 (4H, t, J ¼ 7:3 Hz, NCH2), 8.19
2
(2H, s, Ar); 19F NMR: d 63.81 (d of m, 4F, JSF ÀSF
¼
4
NMR: d 62.56 (d of m, 4F, 2JSF ÀSF ¼ 152:0 Hz, SF4), 84.67
152:1 Hz, SF4), 80.65 (m, 1F, 2JSFÀSF ¼ 152:1 Hz, SF); 13
C
4
4
2
(m, 1F, JSFÀSF ¼ 152:0 Hz, SF); 13C NMR: d 113.4 (qu,
NMR: d 11.1, 20.7, 54.0, 127.7 (s, C-3, C-5), 140.9 (C-2, C-
4
3
2
3JCÀSF ¼ 4:0 Hz, C-3, C-30), 116.0 (qu, JCÀSF ¼ 4:0 Hz,
6), 142.8 (qu, JCÀSF ¼ 22:2 Hz, C-4), 143.9 (C-1). IR
4
4
4
C-5, C-50), 125.4 (s, C-1, C-10), 130.9 (s, C-6, C-60), 144.2 (s,
(Nujol): 3075, 1615, 1539, 1349, 1175, 1113, 980, 911,
860 (S–F), 824 cmÀ1. MS m/z (rel. int.): 393 [M]þ (12), 376
[M À OH]þ (19), 364 [M À Et]þ (81), 348 [M À OEt]þ
(36), 322 [364ÀC3H6]þ (29), 306 [348ÀC3H6]þ (29).
HRMS calcd. for C12H16F5N3O4S, 393.078, found 393.077.
C-2, C-20), 154.8 (qu, JCÀSF ¼ 17:4 Hz, C-4, C-40). IR
2
4
(Nujol): 3433, 3405, 3304, 3205, 1635 (NH), 916, 856,
810 cmÀ1 (S–F). MS m/z (rel. int.): 436 [M]þ (100), 419
[M À NH3]þ (23), 309 [M À SF5]þ (41). HRMS calcd. for
C12H10F10N2S2 436.013, found 436.012. Anal. calcd.: C,
33.03; H, 2.31; N, 6.42; S, 14.70. Found: C, 33.47; H, 2.51;
N, 6.35; S, 14.97.
3.7.2. 2,6-Dinitro-4-pentafluorosulfanyl-N-ethyl-N-n-
butylaniline (13b)
1
Yield 84% as yellow crystals, mp 82–84 8C. H NMR
3.6.4. 2,20-Diamino-6-fluoro-4,40-bis-
pentafluorosulfanylbiphenyl (12b)
(CDCl3): d 0.88 (3H, t, J ¼ 7:2 Hz, CH3), 1.18 (3H, t,
J ¼ 7:2 Hz, CH3), 1.28 (2H, m, CH2), 1.57 (2H, m, CH2),
2.99 (2H, t, J ¼ 7:5 Hz, CH2–N), 3.11 (2H, q, J ¼ 6:8 Hz,
CH2–N), 8.19 (2H, s, Ar). 19F NMR: d 63.37 (d of m, 4F,
Purified by column chromatography on silica gel, eluted
with hexane:benzene 1:2. Yield 88% as slight-yellow solid,
mp 139–141 8C (methanol). 1H NMR (CDCl3): d 3.87 (2H,
broad s, NH2), 6.98 (1H, dd, J ¼ 9:0, 2.0 Hz, Ar), 6.99 (1H,
s, Ar), 7.17 (1H, d, J ¼ 8:7 Hz, Ar), 7.21 (1H, s, Ar), 7.22
(1H, dd, J ¼ 9:0, 2.0 Hz, Ar); 19F NMR: d À110.12 (s, 1F,
JSF ÀSF ¼ 152:4 Hz, SF4), 80.18 (m, 1F, JSFÀSF
¼
4
4
152:4 Hz, SF). MS m/z (rel. int.): 393 [M]þ (8), 376
[M À OH]þ (20), 350 [M À C3H7]þ (100), 334
[M À OC3H7]þ (28), 322 [350ÀC2H4]þ (52), 306
[334ÀC2H4]þ (10). HRMS calcd. for C12H16F5N3O4S,
393.078, found 393.077.
F–Ar), 62.05 (d of m, 4F, 2JSF ÀSF ¼ 150:0 Hz, SF4), 62.49
4
2
(d of m, 4F, JSF ÀSF ¼ 150:0 Hz, SF4), 83.17 (m, 1F,
4

1314
A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
3.7.3. 2,6-Dinitro-4-pentafluorosulfanyl-N-propyl-N-
cyclopropanemethylaniline (13c)
Yield 81% as orange crystals, mp 64–65 8C. H NMR
3.7.7. 2,6-Dinitro-4-trifluoromethylthio-N-propyl-N-
cyclopropanemethylaniline (13g)
1
1
Yield 82% as yellow-orange crystals, mp 54–55 8C. H
NMR (CDCl3): d 0.16 (2H, m, CH2), 0.58 (2H, m, CH2),
0.88 (3H, t, J ¼ 7:5 Hz, CH3), 1.59 (3H, m, CH, CH2), 2.90
(2H, d, J ¼ 6:8 Hz, CH2–N), 3.09 (2H, m, CH2N), 8.21 (2H,
s, Ar). 19F NMR: d À41.87 (s, CF3). MS m/z (rel. int.): 379
[M]þ (7), 362 [M À OH]þ (24), 350 [M À Et]þ (51), 334
[M À OEt]þ (3), 296 [350ÀC4H6]þ (5). HRMS calcd. for
C14H16F3N3O4S 379.081, found 379.079.
(CDCl3): d 0.16 (2H, m, CH2), 0.58 (2H, m, CH2), 0.88 (3H,
t, J ¼ 7:5 Hz, CH3), 1.59 (3H, m, CH, CH2), 2.90 (2H, d,
J ¼ 6:8 Hz, CH2N), 3.09 (2H, m, CH2N), 8.21 (2H, s, Ar);
19F NMR: d 63.39 (d of m, 4F, JSF ÀSF ¼ 151:7 Hz, SF4),
4
80.18 (m, 1F, JSFÀSF ¼ 151:7 Hz, SF); 13C NMR: 4.0, 9.2,
4
3
11.1, 54.1, 57.5, 127.7 (qu, JCÀSF ¼ 4:8 Hz, C-3, C-5),
4
2
141.0 (s, C-2, C-6), 143.1 (qu, JCÀSF ¼ 22:5 Hz, C-4),
4
144.3 (s, C-1). MS m/z (rel. int.): 405 [M]þ (15), 388
[M À OH]þ (74), 376 [M À Et]þ (100), 364 [M À C3H5]þ
(20), 360 [M À OEt]þ (15), 322 [376ÀC4H6]þ (43), 306
[360ÀC4H6]þ (22). HRMS calcd. for C13H16F5N3O4S
405.078, found 405.078.
3.7.8. 2,6-Dinitro-4-trifluoromethylthio-N-ethyl-N-20-
methylallylaniline (13h)
1
Yield 84% as yellow crystals, mp 76–77 8C. H NMR
(CDCl3): d 1.17 (3H, t, J ¼ 7:2 Hz, CH3), 1.73 (3H, s, CH3),
3.10 (2H, q, J ¼ 7:0 Hz, CH2N), 3.53 (2H, s, CH2), 5.0 (2H,
s CH2), 8.19 (2H, s, Ar); 19F NMR: d À41.76 (s, CF3). MS m/
z (rel. int.): 365 [M]þ (20), 348 [M À OH]þ (72), 324
[M À Allyl]þ (28), 308 [M À OAllyl]þ (45), 296
[324ÀC2H4]þ (6). HRMS calcd. for C13H14F3N3O4S
365.063, found 365.060.
3.7.4. 2,6-Dinitro-4-pentafluorosulfanyl-N-ethyl-N-20-
methylallylaniline (13d)
Yield 84% as yellow crystals, mp 64–65 8C. 1H NMR
(CDCl3): d 1.17 (3H, t, J ¼ 7:2 Hz, CH3), 1.73 (3H, s,
CH3), 3.10 (2H, q, J ¼ 7:0 Hz, CH2), 3.53 (2, s, CH2), 5.0
(2H, s, CH2), 8.19 (2H, s, Ar). 19F NMR: d 63.36 (d of m, 4F,
JSF ÀSF ¼ 152:2 Hz, SF4), 80.01 (m, 1F, JSFÀSF ¼ 152:2 Hz,
3.7.9. 2,6-Dinitro-1-piperazino-4-
pentafluorosulfanylbenzene (14a)
Yield 91% as orange-yellow crystals, mp 164–165 8C. H
4
4
SF). MS m/z (rel. int.): 391 [M]þ (20), 374 [M À OH]þ (100),
350 [M À Allyl]þ (36), 334 [M À OAllyl]þ (52), 322
[350ÀC2H4]þ (25), 306 [334ÀC2H4]þ (17). HRMS calcd.
for C12H14F5N3O4S 391.063, found 391.060.
1
NMR (CDCl3): d 2.50 (4H, m, CH2), 3.13 (4H, m, CH2), 8.14
(2H, s, Ar). 19F NMR:
d 63.22 (d of m, 4F,
JSF ÀSF ¼ 152:5 Hz, SF4), 79.62 (m, 1F, JSFÀSF
¼
4
4
3.7.5. 2,6-Dinitro-4-pentafluorosulfanyl-N-propyl-N-
tetrahydrofurfurylaniline (13e)
Yield 77% as orange crystals, mp 66–68 8C. H NMR
(CDCl3): d 0.87 (3H, t, J ¼ 7:4 Hz, CH3), 1.44 (1H, m, CH),
1.64 (2H, m, CH2), 1.83 (2H, m, CH2), 2.01 (1H, m, CH),
2.95 (1H, dd, J ¼ 3:9 Hz, J ¼ 14:4 Hz, CH), 3.07 (2H, m,
CH2), 3.18 (1H, dd, J ¼ 7:2 Hz, J ¼ 14:4 Hz, CH), 3.72
(2H, m, CH2), 4.15 (1H, m, CH), 8.20 (2H, s, Ar). 19F NMR:
152:5 Hz, SF). MS m/z (rel. int.): 378 [M]þ (11), 361
[M À OH]þ
(10),
348
[M À NO]þ
(22),
336
[M À C2H4N]þ (34), 306 [336 À NO]þ (100), 290
[336 À NO2]þ (37), 285 [M À H–2NO2]þ (65), 272
[361 À C2H4N–HNO2]þ (36), 260 [306 À NO2]þ (36), 244
[290 À NO2]þ (42). HRMS calcd. for C10H11F5N4O4S
378.042, found 378.041.
1
d 64.98 (d of m, 4F, JSF ÀSF ¼ 152:2 Hz, SF4), 81.75 (m, 1F,
3.7.10. 2,6-Dinitro-1-N-methylpiperazino-4-
pentafluorosulfanylbenzene (14b)
Yield 91% as yellow crystals, mp 129–131 8C. H NMR
4
JSFÀSF ¼ 152:2 Hz, SF). 13C NMR: d 11.0, 21.1, 25.4, 29.8,
4
1
55.9, 56.2, 68.1, 127.4 (s, C-3, C-5), 141.1 (s, C-2, C-6),
143.7 (qu, 2JCÀSF ¼ 22:8 Hz, C-4), 144.8 (s, C-1). MS m/z
(CDCl3): d 2.34 (3H, s, CH3), 2.50 (4H, m, CH2), 3.14 (4H,
4
(rel. int.): 435 [M]þ (<1), 434 [M À H]þ (<1), 417
[434ÀOH]þ (<1), 363 [434ÀTetrahydrofurfuryl]þ (100),
347 [M À OTetrahydrofurfuryl]þ (21), 321 [363ÀC3H6]þ
(87), 305 [347ÀC3H6]þ (37). HRMS calcd. for
C14H18F5N3O5S 435.089, found 435.086.
m, CH2), 8.14 (2H, s, Ar). 19F NMR: d 63.25 (d of m, 4F,
JSF ÀSF ¼ 152:5 Hz, SF4), 79.62 (m, 1F, JSFÀSF
¼
4
4
152:5 Hz, SF). MS m/z (rel. int.): 392 [M]þ (96), 349
[M À C2H5N]þ (96), 348 [M À H–C2H5N]þ (65), 304
[M À C2H4N–NO2]þ (51), 289 [M À C3H7N–NO2]þ
(100),
273
[M À H–C4H9N–NO2]þ
(49),
258
3.7.6. 2,6-Dinitro-4-trifluoromethylthio-N-ethyl-N-
butylaniline (13f)
[304 À NO2]þ (79), 244 [M À C3H6N–2NO2]þ (78). HRMS
calcd. for C11H13F5N4O4S, 392.058, found 392.057.
Yield 84% as an orange-red solid, mp 56–58 8C. 1H NMR
(CDCl3): d 0.88 (3H, t, J ¼ 7:2 Hz, CH3), 1.18 (3H, t,
J ¼ 7:2 Hz, CH3), 1.28 (2H, m, CH2), 1.57 (2H, m, CH2),
2.98 (2H, t, J ¼ 7:2 Hz, CH2N), 3.10 (2H, q, 6.1 Hz, CH2N),
8.07 (2H, s, Ar); 19F NMR: d À41.90 (s, CF3). MS m/z (rel.
int.): 367 [M]þ (2), 350 [M À OH]þ (6), 324 [M À C3H7]þ
(100), 308 [M À C3H7O]þ (11), 296 [324ÀC2H4]þ (25).
HRMS calcd. for C13H16F3N3O4S 367.081, found 367.082.
3.7.11. 2,6-Dinitro-1-piperazino-4-
trifluoromethylthiobenzene (14c)
Yield 84% as orange-yellow crystals, mp 114–115 8C. 1H
NMR (CDCl3): d 1.72 (1H, s, NH), 2.96 (4H, bs, CH2), 3.07
(4H, bs, CH2N), 8.02 (2H, s, Ar). 19F NMR: d À42.95 (s,
CF3). MS m/z (rel. int.): 352 [M]þ (11), 322 [M À NO]þ
(18), 310 [M À C2H4N]þ (11), 280 [310 À NO]þ (51), 259

A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
1315
[M À H–2NO2]þ (17), 246 [310 À OHÀHNO2]þ (7), 218
3.9. Reactions of 1-chloro-2,6-dinitrobenzene derivatives
with ethyl thioglycolate—general method for the
preparation of 19a–c
[310 À 2NO2]þ (10). HRMS calcd. for C11H11F3N4O4S
352.046, found 352.044.
3.7.12. 2,6-Dinitro-1-piperazino-4-
pentafluoroethylthiobenzene (14d)
Yield 83% as yellow crystals, mp 55–57 8C. H NMR
Triethylamine (1.2 mL, 8.4 mmol) was added to a ice-
cooled mixture of 7.6 mmol of 1-chloro-2,6-dinitroben-
zene derivative (2b,e,f) and 0.91 g (7.6 mmol) of ethyl
thioglycolate (in ethanol). The reaction mixture was stirred
at room temperature for 2 h. The resulting precipitate was
separated by filtration, washed with water and ethanol, and
dried.
1
(CDCl3): d 2.27 (1H, s, NH), 2.98 (4H, q, J ¼ 5:13 Hz,
CH2), 3.09 (4H, q, J ¼ 5:17 Hz, CH2N), 8.03 (2H, s, Ar). 19
F
NMR: d À82.81 (3F, s, CF2CF3), À91.99 (2F, s, CF2CF3).
MS m/z (rel. int.): 402 [M]þ (11), 372 [M À NO]þ (26), 360
[M À C2H4N]þ (10), 330 [360 À NO]þ (46), 309 [M À H–
2NO2]þ (12), 283 [330 À HNO2]þ (11). HRMS calcd. for
C12H11F5N4O4S 402.042, found 402.043.
3.9.1. 2-Ethoxycarbonyl-7-nitro-5-
pentafluorosulfanylbenzothiazole-N-oxide (19a)
Yield 24% as orange crystals, mp 174–176 8C. 1H NMR
(CDCl3): d 1.48 (3H, t, J ¼ 7:0 Hz, CH3), 4.55 (2H, q,
J ¼ 7:0 Hz, CH2), 8.97 (1H, s, Ar), 8.99 (1H, s, Ar). 19F
3.8. Reactions of 1-chloro-2,6-dinitrobenzene derivatives
2b and 2e with potassium ethyl xanthate—general method
for the preparation of 17a and 17b
NMR: d 64.04 (d of m, 4F, JSF ÀSF ¼ 152:2 Hz, SF4), 78.58
4
(m, 1F, JSFÀSF ¼ 152:2 Hz, SF); 13C NMR: d 14.1 (s, CH3),
4
To a solution containing 0.44 g (2.75 mmol) of potas-
sium ethyl xanthate in 3 mL of DMF, 2.5 mmol of 1-
chloro-2,6-dinitrobenzene derivative (2b,e) was added in
one portion. The reaction mixture was heated to 80 8C and
stirred at that temperature for 10 h, after which time it was
stirred for 5 h at room temperature. The solvent Me2NCOH
was then removed under vacuum. The remaining residue
was washed with a 10% solution of hydrochloric acid and
extracted with chloroform. The solvent layer was dried
over Na2SO4 and then evaporated. The resulting residue
was purified by column chromatography (silica, benzene:-
hexane 1:2).
63.5 (s, CH2), 123.4 (qu, 3JCÀSF ¼ 4:9 Hz, C-4), 124.1 (qu,
4
3JCÀSF ¼ 4:8 Hz, C-6), 126.5 (s, C-2), 138.0 (s, C-8), 141.9
4
2
(C-7), 146.3 (C-9), 152.3 (qu, JCÀSF ¼ 22:4 Hz, C-5),
4
156.4 (C¼O). IR (Nujol) 1740 cmÀ1 (C¼O). MS m/z
(rel. int.): 394 [M]þ (10), 378 [M À O]þ (8), 333
[378 À OEt]þ (56), 306 [333 À HCN]þ (100), 260
[306 À NO2]þ (24), 248 [C6H3F5NO2S]þ (12), 201
[248 À NO2]þ (17). HRMS calcd. for C10H7F5N2O5S2
393.972, found 393.971.
3.9.2. 2-Ethoxycarbonyl-7-nitro-5-
trifluoromethylthiobenzothiazole-N-oxide (19b)
Yield 75% as orange crystals, mp 134–136 8C. 1H NMR
(CDCl3): d 1.46 (3H, t, J ¼ 7:2 Hz, CH3), 4.53 (2H, q,
J ¼ 7:2 Hz, CH2), 8.84 (2H, s, Ar); 19F NMR: d À42.03 (s,
CF3); 13C NMR: 14.1 (s, CH3), 63.3 (s, CH2), 125.7 (s, C-5),
126.1 (s, C-2), 128.6 (q, JCÀF ¼ 310:0 Hz, CF3), 132.4 (s, C-
4), 132.7 (s, C-6), 137.4 (s, C-8), 142.4 (s, C-7), 147.0 (C-9),
159.5 (C¼O). IR (Nujol) 1740 cmÀ1 (C¼O). MS m/z (rel.
int.): 368 [M]þ (6), 352 [M À O]þ (39), 333 [352 À F]þ
(14), 322 [M À NO2]þ (30), 307 [352 À OEt]þ (39), 280
[307ÀHCN]þ (100), 250 [280 À HCN]þ (20), 234
[280ÀNO2]þ (27), 222 [250 À CO]þ (13). HRMS calcd.
for C11H7F3N2O5S2 367.975, found 367.976.
3.8.1. 1-Ethylthio-2,6-dinitro-4-
pentafluorosulfanylbenzene (17a)
Yield 9% as orange red crystals, mp 97–99 8C. 1H NMR
(CDCl3): d 1.27 (3H, t, J ¼ 7:4 Hz, CH3), 2.94 (2H, q,
J ¼ 7:4 Hz, CH2), 8.25 (2H, s, Ar). 19F NMR: d 62.98 (d of
2
m, 4F, JSF ÀSF ¼ 152:0 Hz, SF4), 78.12 (1F, m,
4
2JSFÀSF ¼ 152:0 Hz, SF). 13C NMR: d 14.3, 30.9, 124.5
4
(qu, 3JCÀSF ¼ 4:8 Hz, C-3, C-5), 130.9 (s, C-2, C-6), 151.8
4
2
(qu, JCÀSF ¼ 20:0 Hz, C-4), 153.4 (s, C-1). MS m/z (rel.
4
int.): 354 [M]þ (21), 326 [M À C2H4]þ (18), 309
[326 À OH]þ (38), 296 [326 À NO]þ (31), 232
[326 À 2HNO2]þ (100). HRMS calcd. for C8H7F5N2O4S2
353.977, found 353.976.
3.9.3. 2-Ethoxycarbonyl-7-nitro-5-
pentafluoroethylthiobenzothiazole-N-oxide (19c)
3.8.2. 1-Ethylthio-2,6-dinitro-4-trifluoromethylthiobenzene
(17b)
Yield 28% as orange crystals, mp 50–52 8C. H NMR
(CDCl3): 1.26 (3H, t, J ¼ 7:5 Hz, CH3), 2.94 (2H, q,
J ¼ 7:5 Hz, CH2), 8.12 (2H, s, Ar). 19F NMR: d À41.63
(s, CF3). MS m/z (rel. int.): 328 [M]þ (54), 300 [M À C2H4]þ
(32), 283 [300 À OH]þ (67), 270 [300 À NO]þ (73), 223
[300 À HNO2]þ (26), 206 [300 À 2HNO2]þ (100), 176
[M À C2H4S–2HNO2]þ (82). HRMS calcd. for C9H7F3N2-
O4S2 327.980, found 327.978.
Yield 67% as orange crystals, mp 145–147 8C. 1H NMR
(CDCl3): d 1.48 (3H, t, J ¼ 7:2 Hz, CH3), 4.56 (2H, q,
J ¼ 7:2 Hz, CH2), 8.85 (1H, s, Ar), 8.88 (1H, d, J ¼ 1:7 Hz,
Ar). 19F NMR: d À91.15 (s, 2F, CF2CF3), À82.62 (s, 3F,
CF2CF3). IR (Nujol) 1740 cmÀ1 (C¼O). MS m/z (rel. int.):
418 [M]þ (20), 402 [M À O]þ (55), 386 (15), 372
[M À NO2]þ (17), 357 [402 À OEt]þ (48), 346
[M À OEt–HCN]þ (28), 330 [357 À HCN]þ (100), 311
[357 À NO2]þ (14), 284 [330 À NO2]þ (25). HRMS calcd.
for C12H7F5N2O5S2 417.972, found 417.973.
1

1316
A.M. Sipyagin et al. / Journal of Fluorine Chemistry 125 (2004) 1305–1316
[7] Pesticide News No. 52, June 2001, pp. 20–21;
Trifluralin—Fact Sheet, http://www.pan-uk.org/pestnews/Actives/
Triflura.htm (accessed August 2001).
3.10. 7-Nitro-5-trifluoromethylthiobenzothiazol-N-oxide-2-
ylhydroxamic acid (20)
[8] The Georgia Pest Management Newsletter 18, No. 2, 1996;
The Georgia Pest Management Newsletter: The top ten agricultural
pesticides, http://www.ces.uga.edu/Agriculture/entomology/pestnew-
sletter/feb96news.html (accessed August 2001).
A solution of NH2OHꢁHCl (0.11 g, 1.6 mmol) and NaOH
(0.13 g, 3.3 mmol) in methanol was added to a mixture of
0.50 g (1.4 mmol) of 1-ethoxycarbonyl-7-nitro-5-trifluoro-
methylthiobenzothiazole-N-oxide (9b) in methanol. Stirring
was maintained for 5 h, after which the solvent was removed
under vacuum and the remaining residue was dissolved in
water. This aqueous solution was acidified with hydrochloric
acid, and a precipitate formed. The precipitate was collected,
washed with water and methanol, and dried. Yield 52% as
[9] S.C. Stinson, Chem. Eng. News 78 (28) (2000) 63.
[10] S.C. Stinson, Chem. Eng. News 74 (29) (1996) 35.
[11] R.D. Bowden, P.J. Comina, M.P. Greenhall, B.M. Kariuki, A.
Loveday, D. Philp, Tetrahedron 56 (2000) 3399.
[12] P. Kirsch, M. Bremer, A. Taugerbeck, T. Wallmichrath, Angew.
Chem., Int. Ed. Engl. 40 (2001) 1480.
[13] A.M. Sipyagin, C.P. Bateman, Y.-T. Tan, J.S. Thrasher, J. Fluor.
Chem. 112 (2001) 287.
1
orange crystals, mp 229–231 8C. H NMR (Me2SO-d6): d
[14] W.A. Sheppard, J. Am. Chem. Soc. 84 (1962) 3064.
[15] J.E.D. Barton, G. Mitchell, UK Patent GB 2 276 279 (1994).
[16] G.P. Briner, J. Miller, M. Liveris, P.G. Lutz, J. Chem. Soc. (1954)
1265.
8.54 (1H, s, Ar), 8.53 (1H, s, Ar), 11.83 (1H, bs, NH); 19F
NMR: d À42.45 (s, CF3). IR (Nujol): 3450, 3150, 1650 cmÀ1
.
MS m/z (rel. int.): 355 [M]þ (2), 339 [M À O]þ (3), 323
[M À NHOH]þ (12), 305 [323 À H2O]þ (14), 295
[M À CONHOH]þ (15), 280 [323 À O–HCN]þ (53), 275
[295 À HF]þ (27), 250 [280ÀNO]þ (35), 234
[280 À NO2]þ (29). HRMS calcd. for C9H4F3N3O5S2
354.954, found 354.955.
[17] G. Bartoli, P.E. Todesco, Acc. Chem. Res. 10 (1977) 125.
[18] F.A. Carey, R.J. Sundberg (Eds.), Advanced Organic Chemistry, Part
A, Structure and Mechanisms, Plenum Press, NY, 1993, p. 580.
[19] A. Jesih, A.M. Sipyagin, L.F. Chen, W.D. Hong, J.S. Thrasher,
Polym. Prepr. ACS Div. Polym. Chem. 34 (1) (1993) 383.
[20] A.M. Sipyagin, V.S. Enshov, C.P. Bateman, B.D. Mullen, J.S.
Thrasher, in: Book of Abstracts, Proceedings of the 12th European
Symposium on Fluorine Chemistry, Berlin, Germany, September
1998, PII-96.
References
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(1948).
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