Synthesis of aryl perfluoroalkyl sulfides from aromatic disulfides

Article abstract of DOI:10.1023/B:RUCB.0000030820.47938.ab

Thermolysis of xenon(II) bis(perfluoroalkanecarboxylates) in the presence of diaryl disulfides occurs through the S-S bond cleavage to form dihalo-, halonitro-, and halodinitrophenyl perfluoroalkyl sulfides. The latter type of compounds was obtained for the first time. The main side process is the perfluoroalkylation of the aromatic ring.

Full text of DOI:10.1023/B:RUCB.0000030820.47938.ab

420
Russian Chemical Bulletin, International Edition, Vol. 53, No. 2, pp. 420—434, February, 2004
Synthesis of aryl perfluoroalkyl sulfides from aromatic disulfides
A. M. Sipyagin,aꢀ V. S. Enshov,a S. A. Kashtanov,a V. A. Potemkin,b J. S. Thrasher,c and A. Waterfeldc
aInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
18 Institutskii prosp., 143432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (096) 515 5420. Eꢀmail: sip@chgꢀnet.ru
bChelyabinsk State University,
129 Brat´ev Kashirinykh ul., 454136 Chelyabinsk, Russian Federation.
cDepartment of Chemistry, The University of Alabama,
Tuscaloosa, Alabama, Al 35487, USA.
Fax: +1 (205) 348 8448
Thermolysis of xenon(II) bis(perfluoroalkanecarboxylates) in the presence of diaryl disulꢀ
fides occurs through the S—S bond cleavage to form dihaloꢀ, halonitroꢀ, and halodinitrophenyl
perfluoroalkyl sulfides. The latter type of compounds was obtained for the first time. The main
side process is the perfluoroalkylation of the aromatic ring.
Key words: diaryl disulfides, perfluoroalkylation, aryl perfluoroalkyl sulfides.
It is known1 that the substitution of the hydrogen atom
Scheme 1
in aromatic and heterocyclic systems by perfluoroalkyl
groups can substantially change the physical and biologiꢀ
cal properties of molecules. The introduction of "superꢀ
lipophilic" perfluoroalkylthio groups SRF (RF = CF3,
C2F5, etc.) with the highest lipophilicity indices2 can sigꢀ
nificantly change the biological effect of the resulting comꢀ
pounds.3 According to our current scientific interest, we
develop the synthesis of new building blocks containing
both "superlipophilic" groups and substituents capable of
reacting with different nucleophilic agents. These can be,
e.g., halogen atoms or nitro groups in the aromatic and
heterocyclic compounds activated by other electronꢀwithꢀ
drawing substituents.4 In our opinion, this approach can
provide the synthesis of new biologically active comꢀ
pounds.
We developed5,6 a method for the perfluoroalkylation
of thio derivatives of polyhalopyridines based on the therꢀ
molysis of xenon(II) bis(perfluoroalkanecarboxylates).
This method makes it possible to involve accessible startꢀ
ing compounds such as thiols and disulfides, to introduce
the SСnF2n+1 groups (n = 1—3) in high yields, to perform
synthesis under mild conditions and isolate easily target
products, and to synthesize compounds containing groups
sensitive to the nucleophilic attack.
1, 2
R1
R2
R3
R4
1, 2
R1
R2
R3
R4
a
b
c
d
e
f
F
H
H
H
NO2
NO2 Cl
NO2 Cl
H
H
H
H
H
NO2
NO2
NO2
NO2
NO2
H
h
i
j
k
l
m
n
H
H
H
F
Cl
H
H
H
NO2
H
H
H
Br
H
NO2
H
H
H
H
H
H
Br
CF3
Cl
H
Cl
Br
H
H
H
Cl
Cl
g
Cl
H
Cl
Cl
As a rule, xenon(II) bis(perfluoroalkanecarboxylates)
were generated in a preliminary step by mixing equimolar
amounts of XeF2 and perfluoroalkanecarboxylic acid in
CH2Cl2 on cooling (method A). Alternatively, method B
involved the in situ addition of XeF2 to a solution or
suspension of a disulfide in perfluoroalkanecarboxylic acid.
The mode of conducting the subsequent reaction was
determined by both the solubility of the starting disulfides
2a—n and temperatures of decomposition of xenon
bis(perfluoroalkanecarboxylates) upon the generation of
In the present work, we successfully used the method
for a series of aromatic compounds. The starting comꢀ
pounds were diaryl disulfides 2a—n (Tables 1 and 2), the
most part of which (except 2i,j) were synthesized7—9 by
the reduction of the respective sulfonyl chlorides 1 with a
solution of НBr in acetic acid in the presence of phenol as
an acceptor of liberated Br2 (Scheme 1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 402—415, February, 2004.
1066ꢀ5285/04/5302ꢀ0420 © 2004 Plenum Publishing Corporation

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
421
Table 1. Yields and melting points of diaryl disulfides 2a—h,k—n
3a—n and the arylthiyl radicals. The recombination of the
RS• and •RF radicals also affords the expected derivaꢀ
tives 3a—n.5
Comꢀ Yield
pound
M.p./°С
(Refs.)
Comꢀ Yield
pound
M.p./°С
(Refs.)
2a
2b
82.0
85.0
124—126
142—144
2g
2h
73.5
89.0
77—79
(81—82)14
92—94
Scheme 2
(143—144)9
160—162
(RFCOO)2Xe
RSSR + •RF
Xe + 2 CO2 + 2 •RF
RSRF + RS•
2c
2d
90.0
83.0
(89—90)14
40—41
(159—161)12
185—187
(186—187)13
190—192
117—119
(116—117)9
2k
2l
2m
2n
84.0
80.0
77.5
90.0
55—57
78—79
87—89
(89—90)15
RS• + •RF
RSRF
2e
2f
90.0
88.0
3a—n
R = Aryl, RF = CnF2n+1 (n = 1—3)
In several cases, we succeeded in isolating individual
components of the reaction mixtures obtained upon the
reactions of disulfides 2 with xenon bis(perfluoroalkaneꢀ
carboxylates). If the preparative separation of the reaction
products was inefficient, the GCꢀMS method was used
for the analysis. The main components of the reaction
mixtures are the respective dihaloꢀ, halonitroꢀ, and
halodinitrophenyl perfluoroalkyl sulfides 3—5 (Scheme 3).
Their yields can achieve 70% when molecules of the startꢀ
ing disulfides contained several electronꢀwithdrawing subꢀ
stituents (for example, compound 3e).
perfluoroalkyl radicals. For example, xenon bis(trifluoroꢀ
acetate) is noticeably decomposed in a СН2Cl2 solution
even at temperatures about 0 °С, whereas heptafluoroꢀ
butyrate needs heating to 40—50 °С. Therefore, the C3F7S
derivatives were usually synthesized in the corresponding
perfluoroalkanecarboxylic acid.
The thermolysis of the xenon compounds in the presꢀ
ence of diaryl disulfides 2a—n produces aryl perfluoroalkyl
sulfides. This process is presented in Scheme 2. Freeꢀ
radical substitution of the RS moieties in aromatic disulꢀ
fides RSSR under the action of perfluoroalkyl radicals
formed upon the thermolysis of xenon bis(perfluoroꢀ
alkanecarboxylates) results in aryl perfluoroalkyl sulfides
Insertion of one or two perfluoroalkyl radicals into the
benzene ring with the simultaneous formation of aryl
perfluoroalkyl sulfides represent side processes. The reacꢀ
Table 2. Data on the 1Н and 13C NMR spectra, mass spectra, and highꢀresolution mass spectra of disulfides 2a,k—m
Comꢀ
pound
NMR (δ, J/Hz)
MS,
m/z (Irel (%))
Highꢀresolution mass spectrum
δ
δ
Found,
Molecular
formula
Calculated,
H
C
m/z [M]+
M
2a
2k
7.27 (m, Н(6)),
8.19 (m, Н(4)),
8.53 (m, Н(3))
117.0 (d, J = 24.3),
125.3 (d, J = 19.7),
125.8 (d, J = 9.4),
126.5, 144.7 (br.s),
163.7 (d, J = 257.8)
117.2 (d, J = 3.5),
117.5 (d, J = 23.2),
125.4 (d, J = 18.8),
132.8 (d, J = 7.7),
133.4, 159.6 (d,
J = 248.0)
344 [M]+ (92), 173 [M/2 + 1]+ (100),
356 [M/2]+ (32),
343.974
C12H6F2O4S2
343.974
126 [M/2 – NO2]+ (95)
6.96 (t, Н(3),
J = 8.8),
7.38 (m, H(4)),
7.69 (dd, Н(6),
J = 2.4)
414 (41), 412 (75) and 410 [M]+ (40),
207 (27), 205 [M/2]+ (26), 126 (100)
413.821
409.825
C12H681Br2F2S2 413.822
C12H679Br2F2S2 409.826
2l
7.48 (dd, (H(3),
—
422 [M]+ (100), 403 [M – F]+ (11),
352 [M – 2 Cl]+ (6), 211 [M/2]+ (73),
176 [M/2 – Cl]+ (35),
421.919
353.865
С14H6Cl2F6S2
421.919
353.867
4
H(4), JH,H
=
3.0, 3JH,H = 8.5),
7.86 (s, H(6))
157 [M/2 – Cl – F]+ (14),
142 [M/2 – CF3]+ (14), 69 [CF3]+ (7)
356 [M]+ (100), 321 [M – Cl]+ (5),
286 [M – 2 Cl]+ (41),
2m
7.23 (t, H(4),
4JH,H = 1.7),
7.34 (d, H(2),
—
C12H6Cl4S2
251 [M – 3 Cl]+ (2), 178 [М/2]+ (40),
142 [M/2 – HCl]+ (58),
4
H(6), JH,H = 1.7)
107 [M/2 – HCl – Cl]+ (9)

422
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Scheme 3
n = 1 (3, 6, 9), 2 (4, 7, 10), 3 (5, 8)
Comꢀ
R1
R2
R3
R4
Comꢀ
R1
R2
R3
R4
Comꢀ
R1
R2
R3
R4
R5
pound
pound
pound
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
F
H
H
H
NO2
NO2
NO2
H
H
NO2
H
H
H
H
H
Cl
Cl
H
Br
H
NO2
H
H
NO2
NO2
NO2
NO2
NO2
H
Cl
H
H
H
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
F
H
H
H
NO2
NO2
NO2
H
H
NO2
H
H
H
H
H
Cl
Cl
H
Br
H
NO2
H
H
NO2
NO2
NO2
NO2
NO2
H
Cl
H
H
H
5a
5b
5c
5d
5e
5f
6a
6b
6c
6d
7a
7b
7c
F
H
H
H
NO2
H
Cl
H
*
Cl
Cl
**
Cl
Cl
H
H
H
H
NO2
NO2
NO2
NO2
Br
H
Br
CF3
Cl
*
—
—
—
—
—
—
H
*
*
*
Cl
Br
H
H
H
Cl
H
H
H
F
Cl
Br
H
H
H
Cl
H
H
H
F
Cl
Br
H
F
H
F
Cl
*
*
H
Cl
CF3
*
*
Cl
**
**
Cl
H
H
Cl
Cl
Br
CF3
Cl
H
H
Cl
Cl
Br
CF3
Cl
Cl
**
**
**
Cl
**
CF3
**
**
Cl
H
H
Cl
H
H
H
Cl
H
Cl
H
H
* 6: Rm = H, H, CF3; m = 2, 3, 5 (b), 1, 3, 5 (c), 1, 4, 5 (d). ** 7: Rm = H, H, C2F5; m = 2, 3, 5 (a), 1, 3, 5 (b), 1, 4, 5 (c)
8: R1, R4, R5 = H, H, C3F7; R2 = R3 = Cl; 9: R1 = F; R2, R3, R5 = H, H, CF3; R4 = Br (a); R1, R4, R5 = H, H, CF3; R2 = R3 = Cl (b)
10: R1, R4, R5 = H, H, C2F5; R2 = R3 = Cl
tion mixtures can contain two or three isomers of monoꢀ
substituted derivatives (11—17). We failed to separate preꢀ
paratively monosubstitution products 6b—d, 7а,b, and 8
into individual isomers and to isolate disubstituted deꢀ
rivatives 9a,b and 10. Therefore, in the case of disulfides
2k—n, the reaction mixtures were studied by GCꢀMS
(Table 3).
It was found that if the paraꢀposition of the benzene
ring is occupied by a substituent (halogen atom or nitro
group), the insertion of perfluoroalkyl radicals is not seꢀ
lective and results in a set of products of monosubstituꢀ
tion at all free positions. For example, in the case of
disulfide 2n, all three possible isomers 15—17 were
found in the reaction mixture by GCꢀMS. The degree
of perfluoroalkylation of the aromatic fragment deꢀ
creases when several electronꢀwithdrawing substituents
are present. Thus, no byꢀproducts were found in the reacꢀ
tion mixture in the case of dinitrochloro derivative 3e. In
the case of disulfides 2a—d,g,i,k containing no paraꢀsubꢀ
stituents with respect to the —S—S— group, we observed
the predominant perfluoroalkylation of the aromatic ring
at position 4 with respect to the perfluoroalkylthio group
with the formation of isomers 11—13. For several reacꢀ
tion mixtures, these derivatives were preparatively isoꢀ
lated and characterized by a complex of physicochemical
methods (Tables 4—6). At the same time, in these cases
too, the presence of isomer 14 was confirmed by both
GCꢀMS and isolation in the individual state. The mechaꢀ
nism of perfluoroalkylation at position 4 can be presented
as follows (Scheme 4): the interaction of diaryl disulfide 2
with the perfluoroalkyl radical generates arylthiyl radiꢀ
cal 18, which is further isomerized to carbonꢀcentered
radical 19 with the localization of the radical center in
position 4 of the benzene ring. Its subsequent recombinaꢀ
tion with the perfluoroalkyl radical affords 4ꢀperfluoroꢀ
alkylꢀsubstituted benzenethiol (20), which is further transꢀ
formed, in the presence of xenon bis(perfluoroalkaneꢀ
carboxylate), into the respective disulfide 21 and then
into derivatives 11—13 (see Scheme 4).
Note that the degree of perfluoroalkylation of the benꢀ
zene ring decreases in the case of heptafluoropropyl radiꢀ
cals, which can evidently be related to both differences in
energy characteristics of intermediates and the influence
of steric factors on their insertion into the aromatic ring.
Ab initio quantumꢀchemical calculations in the
STOꢀ3G basis set were carried out for some intermediates

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
423
Table 3. Data on GCꢀMS analysis of the composition of reaction mixtures obtained from disulfides 2k—n
Disulꢀ
fide
Composition Molecular
τ*
/min
MS, m/z (Irel(%))***
of reaction
formula
mixture** (%)
2k
1 (1) 3k (56.4) C7H3BrF4S
(2) 6a (39.7) С8H2BrF7S
4.66
3.99
274 [M]+ (100), 255 [M – F]+ (3), 205 [M – CF3]+ (39),
176 [M – F – Br]+ (8), 126 [M – CF3 – Br]+ (100), 69 [CF3]+ (47)
342 [M]+ (87), 273 [M – CF3]+ (19), 254 [M – CF3 – F]+ (5),
194 [M – CF3 – Br]+ (100), 175 [M – CF3 – F – Br]+ (19),
93 [M – SCF3 – CF3 – Br]+ (9), 69 [CF3]+ (67)
(3) 9a (3.9)
C9HBrF10
S
4.32
410 [M]+ (57), 391 [M – F]+ (13), 322 [M – F – CF3]+ (26),
262 [M – CF3 – Br]+ (89), 193 [M – 2 CF3 – Br]+ (21),
161 [M – CF3 – SCF3 – Br]+ (14), 99 [M – 2 CF3 – SCF3 – Br]+ (13),
69 [CF3]+ (100)
2l
2 (1) 3l (63.2) C8H3ClF6S
(2) 6b (13.7) С9H2ClF9S
2.83
2.53
280 [M]+ (100), 261 [M – F]+ (23), 211 [M – CF3]+ (66),
176 [M – CF3 – Cl]+ (31), 157 [M – CF3 – Cl – F]+ (13),
142 [M – 2 CF3]+ (12), 107 [M – 2 CF3 – Cl]+ (3), 69 [CF3]+ (24)
348 [M]+ (100), 329 [M – F]+ (23), 293 [M – F – Cl]+ (1),
279 [M – CF3]+ (29), 225 [M – CF3 – Cl – F]+ (29),
210 [M – 2 CF3]+ (15), 175 [M – 2 CF3 – Cl]+ (4),
106 [M – 3 CF3 – Cl]+ (3), 69 [CF3]+ (17)
(2) 6b (23.1)
2.78
348 [M]+ (100), 329 [M – F]+ (23), 313 [M – Cl]+ (1),
279 [M – CF3]+ (29), 244 [M – CF3 – Cl]+ (10),
225 [M – CF3 – Cl – F]+ (16), 175 [M – 2 CF3 – Cl]+ (4),
106 [M – 3 CF3 – Cl]+ (3), 69 [CF3]+ (17)
3 (1) 4l (44.1) C9H3ClF8S
2.90
2.55
2.83
3.68
3.85
330 [M]+ (100), 261 [M – CF3]+ (46), 211 [M – C2F5]+ (65),
176 [M – C2F5 – Cl]+ (33), 142 [M – C2F5 – CF3]+ (12),
119 [C2F5]+ (8), 69 [CF3]+ (18)
(2) 7a (19.1)
(2) 7a (25.9)
С
11H2ClF13
S
448 [M]+ (93), 379 [M – CF3]+ (100), 329 [M – C2F5]+ (26),
310 [M – 2 CF3]+ (7), 225 [M – C2F5 – CF3 – Cl]+ (45),
119 [C2F5]+ (7), 69 [CF3]+ (17)
448 [M]+ (55), 379 [M – CF3]+ (100), 329 [M – C2F5]+ (9),
260 [M – C2F5 – CF3]+ (44), 119 [C2F5]+ (6),
106 [M – 2 C2F5 – CF3 – Cl]+ (2), 69 [CF3]+ (15)
246 [M]+ (100), 227 [M – F]+ (6), 211 [M – Cl]+ (2),
177 [M – CF3]+ (44), 142 [M – CF3 – Cl]+ (41),
107 [M – CF3 – 2 Cl]+ (9), 69 [CF3]+ (16)
314 [M]+ (100), 279 [M – Cl]+ (2), 245 [M – CF3]+ (27),
226 [M – CF3 – F]+ (12), 210 [M – CF3 – Cl]+ (30),
175 [M – CF3 – 2 Cl]+ (9), 143 [M – SCF3 – 2 Cl]+ (4),
106 [M – 2 CF3 – 2 Cl]+ (4), 69 [CF3]+ (14)
2m
4 (1) 3m (52.4) C7H3Cl2F3S
(2) 6c (47.6) С8H2Cl2F6S
5 (1) 4m (58.1) С8H3Cl2F5S
3.40
3.80
296 [M]+ (100), 227 [M – CF3]+ (36), 207 [M – F – 2 Cl]+ (1),
192 [M – CF3 – Cl]+ (3), 177 [M – C2F5]+ (43),
142 [M – C2F5 – Cl]+ (53), 119 [C2F5]+ (9),
107 [M – C2F5 – 2 Cl]+ (13), 69 [CF3]+ (20)
414 [M]+ (46), 395 [M – F]+ (5), 345 [M – CF3]+ (100),
295 [M – C2F5]+ (4), 276 [M – 2 CF3]+ (5),
226 [M – C2F5 – CF3]+ (38), 191 [M – C2F5 – CF3 – Cl]+ (22),
176 [M – 2 C2F5]+ (8), 159 [M – SC2F5 – CF3 – Cl]+ (4),
119 [C2F5]+ (6), 69 [CF3]+ (14)
(2) 7b (41.9)
С10H2Cl2F10S
2n
6 (1) 3n (43.2) C7H3Cl2F3S
(2) 6d (14.9) C8H2Cl2F6S
5.50
4.87
246 [M]+ (100), 227 [M – F]+ (6), 211 [M – Cl]+ (0.5),
192 [M – Cl – F]+ (1), 177 [M – CF3]+ (84),
142 [M – CF3 – Cl]+ (71), 107 [M – CF3, – 2 Cl]+ (16),
69 [CF3]+ (36)
314 [M]+ (100), 295 [M – F]+ (15), 245 [M – CF3]+ (56),
210 [M – CF3 – Cl]+ (44), 175 [M – CF3 – 2 Cl]+ (38),
143 [M – SCF3 – 2 Cl]+ (5) 106 [M – 2 CF3 – 2 Cl]+ (12),
69 [CF3]+ (53)
(to be continued)

424
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Table 3 (continued)
Disulꢀ
fide
Composition Molecular
τ*
/min
MS, m/z (Irel(%))***
of reaction
formula
mixture** (%)
(2) 6d (19.0)
(2) 6d (10.9)
(3) 9b (4.5)
5.62
6.94
4.68
314 [M]+ (100), 295 [M – F]+ (15), 260 [M – F – Cl]+ (1),
245 [M – CF3]+ (62), 210 [M – CF3 – Cl]+ (15),
143 [M – SCF3 – 2 Cl]+ (2), 106 [M – 2 CF3 – 2 Cl]+ (15),
69 [CF3]+ (41)
314 [M]+ (100), 295 [M – F]+ (12), 279 [M – Cl]+ (1),
245 [M – Cl]+ (50), 175 [M – CF3 – 2 Cl]+ (16),
143 [M – SCF3 – 2 Cl]+ (6), 106 [M – 2 CF3 – 2 Cl]+ (44),
69 [CF3]+ (78)
382 [M]+ (100), 363 [M – F]+ (61), 313 [M – CF3]+ (61),
278 [M – CF3 – Cl]+ (47), 244 [M – 2 CF3]+ (23),
209 [M – Cl – 2 CF3]+ (9), 174 [M – 2 CF3 – 2 Cl]+ (6),
105 [M – 3 CF3 – 2 Cl]+ (7), 69 [CF3]+ (68)
296 [M]+ (100), 277 [M – F]+ (8), 227 [M – CF3]+ (8),
177 [M – C2F5]+ (95), 142 [M – C2F5, – Cl]+ (62),
119 [C2F5]+ (18), 69 [CF3]+ (36)
C9HCl2F9S
7 (1) 4n (59.0) C8H3Cl2F5S
(2) 7c (16.1) С10H2Cl2F10
5.73
4.34
S
414 [M]+ (100), 395 [M – F]+ (8), 345 [M – CF3]+ (55),
295 [M – C2F5]+ (58), 226 [M – C2F5 – CF3]+ (37),
191 [M – C2F5 – CF3 – Cl]+ (44), 159 [M – SC2F5 – CF3 – Cl]+ (8),
119 [C2F5]+ (25), 69 [CF3]+ (56)
(2) 7c (14.8)
(2) 7c (7.4)
5.04
6.16
414 [M]+ (100), 395 [M – F]+ (7), 345 [M – CF3]+ (59),
295 [M – C2F5]+ (53), 260 [M – C2F5 – Cl]+ (15),
226 [M – C2F5 – CF3]+ (15), 159 [M – SC2F5 – CF3 – Cl]+ (5),
119 [C2F5]+ (19), 69 [CF3]+ (41)
414 [M]+ (100), 395 [M – F]+ (8), 345 [M – CF3]+ (40),
310 [M – CF3 – Cl]+ (15), 295 [M – C2F5]+ (65),
260 [M – C2F5 – Cl]+ (45), 226 [M – C2F5 – CF3]+ (38),
191 [M – C2F5 – CF3 – Cl]+ (44), 119 [C2F5]+ (31), 69 [CF3]+ (78)
(3) 10 (3.9)
C
12HCl2F15
S
3.33
6.25
532 [M]+ (55), 413 [M – C2F5]+ (80), 294 [M – 2 C2F5]+ (75),
262 [M – C2F5 – SC2F5]+ (89), 225 [M – 2 C2F5 – CF3]+ (59),
193 [M – SC2F5 – C2F5 – CF3]+ (94), 119 [C2F5]+ (78), 69 [CF3]+ (100)
346 [M]+ (100), 327 [M – F]+ (7), 292 [M – F – Cl]+ (2),
258 [M – F – CF3]+ (1), 227 [M – C2F5]+ (27),
8 (1) 5f (58.7) C7H3Cl2F3S
192 [M – Cl – C2F5]+ (2), 177 [M – C3F7]+ (93),
142 [M – C3F7, – Cl]+ (68), 107 [M – C3F7 – 2 Cl]+ (16),
69 [CF3]+ (51)
(2) 8 (14.3)
C12H2Cl2F14
S
5.68
514 [M]+ (56), 495 [M – F]+ (13), 460 [M – F – Cl]+ (1),
395 [M – C2F5]+ (85), 345 [M – C3F7]+ (29),
326 [M – C2F5 – CF3]+ (10), 226 [M – C3F7 – C2F5]+ (93),
191 [M – C3F7 – C2F5 – Cl]+ (53), 159 [M – SC3F7, – C2F5 – Cl]+ (15),
106 [M – 2 C3F7 – 2 Cl]+ (15), 69 [CF3]+ (100)
(2) 8 (14.3)
(2) 8 (12.8)
5.89
6.83
514 [M]+ (56), 395 [M – C2F5]+ (91), 345 [M – C3F7]+ (40),
326 [M – C3F7 – F]+ (10), 226 [M – C2F5 – C3F7]+ (43),
159 [M – SC3F7 – C2F5 – Cl]+ (10), 119 [C2F5]+ (13), 69 [CF3]+ (100)
514 [M]+ (100), 495 [M – F]+ (15), 395 [M – C2F5]+ (62),
345 [M – C3F7]+ (32), 326 [M – C2F5 – CF3]+ (23),
226 [M – C2F5 – C3F7]+ (40), 191 [M – C3F7 – C2F5 – Cl]+ (17),
159 [M – SC3F7 – C2F5 – CF3 – Cl]+ (4), 119 [C2F5]+ (3), 69 [CF3]+ (23)
* τ is the retention time.
** (1) ArSRF, (2) monosubstitution product, (3) disubstitution product.
*** Hereinafter the m/z values are presented for ions with 35Cl and 79Br.

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
425
Scheme 4
n = 1 (11, 14, 15a, 16a, 17a), 2 (12, 15b, 16b, 17b),
3 (13, 15c, 16c, 17c))
18 R1
R2
R3
R4
18 R1
R2
R3
R4
Comꢀ
R1
R2
R4
Comꢀ
R1
R2
R4
a
b
c
d
e
f
F
H
H
H
NO2
NO2 Cl
NO2 Cl
H
H
H
H
H
NO2
NO2
NO2
NO2
NO2
H
h
i
j
k
l
H
H
H
F
Cl
H
H
H
H
H
H
H
Cl
Cl
Br
H
NO2
H
H
H
H
NO2
H
Br
CF3
Cl
pound
pound
Cl
Br
H
H
H
11a
11b
11c
11d
11e
F
H
H
H
NO2
H
NO2
NO2
NO2
NO2
Cl
12a
12b
12c
13
Cl
H
F
H
NO2
H
Cl
H
Br
Br
Cl
Br
H
F
H
m
n
Cl
g
Cl
H
Cl
Cl
H
14: R1 = Cl (a), Br (b); R3 = H, R4 = NO2
15, 16: R2 = R3 = Cl, R4 = H; 17: R1 = H, R2 = R3 = Cl
mined by the СS wavefunction coefficient of the radiꢀ
cal ArS•.
Different regularities were revealed from the analysis
of the results of calculation of reactive species 18a—d,g,i,k
for R3 = H. It is found that trifluoromethylation is deterꢀ
mined by a set of energy and charge characteristics and,
to a great extent, by the energy of the higher occupied
βꢀorbital of the sulfur atom10 (Table 8). The general equaꢀ
tion relating the yield of ArSRF and the calculated quanꢀ
tum characteristics was established to take the form
that can be involved in perfluoroalkylation. In the case of
radicals 18e,f,h,j with the substituent R3 ≠ H, we found a
dependence of the yield of the target product on the
wavefunction coefficient (СS) of the sulfur atom for the
highest occupied αꢀorbital at spin multiplicity 2. This
coefficient characterizes the density of probability of the
localization of unpaired electron, which ensures the addiꢀ
tion of the electrophilic perfluoroalkyl radical10 to the
sulfur atom (Table 7). The general equation relating the
yield of the ArSRF products and CS coefficient has the
form
LUMO
Y(ArSRF) = –389 – 68ЕβHOMO – 169Еβ
–
– 640QCS – 710QH(4)
,
(2)
where ЕβHOMO and ЕβLUMO are the energies of the HOMO
and LUMO βꢀorbitals, QCS is the charge on the carbon
atom of the benzene ring linked with the thio group, and
QH(4) is the charge on the hydrogen atom that is in the
paraꢀposition to the thio group and has multiplicity 4.
In this case, the formation of the byꢀproduct should
directly be related to the probability of radical center loꢀ
calization in the paraꢀposition to the thio group (interꢀ
mediate 18). The contribution of this structure is deterꢀ
Y(ArSRF) = 68.4 – 63.2CS,
(1)
Y is the yield of ArSRF.
It is seen from Eq. (1) that a decrease in СS, which can
appear when the benzene ring of reacting species 18 conꢀ
tains electronꢀwithdrawing substituents, increases the yield
of the target product, which is the case. It should be noted
that the yield of the target product depends slightly on the
nature of the perfluoroalkyl radical but is mainly deterꢀ

426
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Table 4. Method of synthesis, yields, and physicochemical characteristics of compounds 3a—j, 4a—k, 5a—e, 11a—e, 12a—c, 13,
and 14a,b
Compound
Method
of synthesis (%)
Yield
B.p./°C
(p/Torr),
[M.p./°C]
1ꢀFluoroꢀ4ꢀnitroꢀ2ꢀ(trifluoromethylthio)benzene (3а)
1ꢀChloroꢀ4ꢀnitroꢀ2ꢀ(trifluoromethylthio)benzene (3b)
B
А
33.6
24.5
Oil,
140 (8)16
Oil,
126—129 (16 mTorr)17
Oil
1ꢀBromoꢀ4ꢀnitroꢀ2ꢀ(trifluoromethylthio)benzene (3c)
1,3ꢀDinitroꢀ5ꢀ(trifluoromethylthio)benzene (3d)
2ꢀChloroꢀ1,3ꢀdinitroꢀ5ꢀ(trifluoromethylthio)benzene(3e)
1ꢀChloroꢀ2ꢀnitroꢀ4ꢀ(trifluoromethylthio)benzene (3f)
1,4ꢀDichloroꢀ2ꢀ(trifluoromethylthio)benzene (3g)
1ꢀBromoꢀ4ꢀ(trifluoromethylthio)benzene (3h)
1ꢀNitroꢀ3ꢀ(trifluoromethylthio)benzene (3i)
А
А
А
А
А
А
А
А
34.7
30.0
73.0
16.1
22.5
24.6
7.8
Oil (oil18
[36—38]
Oil
Oil
Oil, 192 19
Oil
Oil,
120 (20)20
Oil
Oil
Oil
[66—67]
Oil
)
1ꢀNitroꢀ4ꢀ(trifluoromethylthio)benzene (3j)
15.2
1ꢀFluoroꢀ4ꢀnitroꢀ2ꢀ(pentafluoroethylthio)benzene (4a)
1ꢀChloroꢀ4ꢀnitroꢀ2ꢀ(pentafluoroethylthio)benzene (4b)
1ꢀBromoꢀ4ꢀnitroꢀ2ꢀ(pentafluoroethylthio)benzene (4c)
1,3ꢀDinitroꢀ5ꢀ(pentafluoroethylthio)benzene (4d)
2ꢀChloroꢀ1,3ꢀdinitroꢀ5ꢀ(pentafluoroethylthio)benzene (4e)
1ꢀChloroꢀ2ꢀnitroꢀ4ꢀ(pentafluoroethylthio)benzene (4f)
1,4ꢀDichloroꢀ2ꢀ(pentafluoroethylthio)benzene (4g)
1ꢀBromoꢀ4ꢀ(pentafluoroethylthio)benzene (4h)
1ꢀNitroꢀ3ꢀ(pentafluoroethylthio)benzene (4i)
B
А
А
А
А
А
А
А
А
А
B
А
А
А
А
B
B
А
А
А
А
А
А
B
B
А
A
55.3
37.7
40.2
14.7
66.4
16.9
13.3
34.1
8.1
30.3
23.0
33.0
26.7
27.3
19.0
16.7
6.7
7.8
8.8
1.7
3.4
5.2
4.4
9.1
5.4
Oil
Oil
Oil
Oil
1ꢀNitroꢀ4ꢀ(pentafluoroethylthio)benzene (4j)
[37—38]
Oil
Oil
[28—29]
Oil
4ꢀBromoꢀ4ꢀfluoroꢀ3ꢀ(pentafluoroethylthio)benzene (4k)
1ꢀFluoroꢀ2ꢀ(heptafluoropropylthio)ꢀ4ꢀnitrobenzene (5а)
1ꢀChloroꢀ2ꢀ(heptafluoropropylthio)ꢀ4ꢀnitrobenzene (5b)
1ꢀBromoꢀ2ꢀ(heptafluoropropylthio)ꢀ4ꢀnitrobenzene (5c)
5ꢀ(Heptafluoropropylthio)ꢀ1,3ꢀdinitrobenzene (5d)
1ꢀBromoꢀ4ꢀfluoroꢀ2ꢀ(heptafluoropropylthio)benzene (5e)
1ꢀFluoroꢀ4ꢀnitroꢀ5ꢀtrifluoromethylꢀ2ꢀ(trifluoromethylthio)benzene (11a)
1ꢀChloroꢀ4ꢀnitroꢀ5ꢀtrifluoromethylꢀ2ꢀ(trifluoromethylthio)benzene (11b)
5ꢀBromoꢀ2ꢀnitroꢀ1ꢀtrifluoromethylꢀ4ꢀ(trifluoromethylthio)benzene (11c)
1,3ꢀDinitroꢀ2ꢀtrifluoromethylꢀ5ꢀ(trifluoromethylthio)benzene (11d)
1,4ꢀDichloroꢀ5ꢀtrifluoromethylꢀ2ꢀ(trifluoromethylthio)benzene (11e)
1,4ꢀDichloroꢀ2ꢀpentafluoroethylꢀ5ꢀ(pentafluoroethylthio)benzene (12a)
1ꢀNitroꢀ2ꢀpentafluoroethylꢀ5ꢀ(pentafluoroethylthio)benzene (12b)
1ꢀBromoꢀ4ꢀfluoroꢀ2ꢀpentafluoroethylꢀ5ꢀ(pentafluoroethylthio)benzene (12c)
1ꢀBromoꢀ4ꢀfluoroꢀ2ꢀheptafluoropropylꢀ5ꢀ(heptafluoropropylthio)benzene (13)
1ꢀChloroꢀ5ꢀnitroꢀ2ꢀtrifluoromethylꢀ3ꢀ(trifluoromethylthio)benzene (14a)
1ꢀBromoꢀ5ꢀnitroꢀ2ꢀtrifluoromethylꢀ3ꢀ(trifluoromethylthio)benzene (14b)
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
Oil
3.3
1.5
Oil
mined by both the charges on atoms linked with the radical
ArSRF (RF = C2F5 and C3F7) was found to depend on the
charge characteristics (charges on sulfur, carbon of the
benzene ring linked with the thio group, and hydrogen
atom in the paraꢀposition to the thio group) and to be
independent of the energy characteristics (Table 9). The
general equation has the form
LUMO
center and energy characteristics of ЕβHOMO and Еβ
.
The introduction of electronꢀwithdrawing substituents
should favor a decrease in both the HOMO and LUMO
energies10 and the QCS and QH(4) charges and, correꢀ
spondingly, should decrease the probability of side proꢀ
cesses related to the perfluoroalkylation of the benzene
ring. As a consequence, the yield of the ArSRF comꢀ
pounds should be enhanced.
Y(ArSRF) = –373 + 1040QS – 1300QCS + 970QH,
(3)
where QS is the charge on the sulfur atom, and QН is the
charge on the Н(4) atom in the paraꢀposition to the thio
group in the state with multiplicity 2.
Unlike the yields in trifluoromethylation reactions,
the yield of compounds 4 and 5 with the general formula

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
427
1
Table 5. Data on the H and 19F NMR spectra and mass spectra of compounds 3a—j, 4a—k, 5a—e, 11a—e, 12a—c, 13, and 14a,b
Comꢀ
pound
NMR (δ, J/Hz)
MS, m/z (Irel (%))
1H
19F
3a 7.40 (dd, 1 H, H(6), 3JH,H = 9.1,
3JH,F = 7.3); 8.43 (m, 1 H, H(5));
8.61 (dd, 1 H, H(3), 4JH,F = 5.9,
4JH,H = 2.8)
3b 7.75 (d, 1 H, H(6), 3JH,H = 8.9);
8.28 (dd, 1 H, H(5), 3JH,H = 8.9,
4JH,H = 2.7); 8.62 (d, 1 H, H(3),
4JH,H = 2.7)
3c 7.94 (d, 1 H, H(6), 3JH,H = 8.9);
8.18 (dd, 1 H, H(5), 3JH,H = 8.9,
4JH,H = 2.7); 8.61 (d, 1 H, Н(3),
4JH,H = 2.4)
–93.90 (m, 1 F,
F—Ar); –42.12 (d,
3 F, СF3,
241 [M]+ (100), 222 [M – F]+ (6),
195 [M – NO2]+ (9), 172 [M – CF3]+ (5),
126 [M – NO2, – CF3]+ (44), 69 [CF3]+ (17)
5JCF ,F = 5.1)
3
–41.75 (s, CF3)
257 [M]+ (100), 238 [M – F]+ (4), 211 [M – NO2]+
(8), 176 [M – NO2 – Cl]+ (7), 142 [M – NO2 – CF3]+
(23), 107 [M – NO2 – CF3 – Cl]+ (16),
75 [C6H3]+ (3), 69 [CF3]+ (15)
–41.78 (s, CF3)
301 [M]+ (70), 282 [M – F]+ (3),
176 [M – Br – NO2]+ (61), 153 [M – CF3 – Br]+ (4),
107 [M – Br – NO2 – CF3]+
(59), 69 [CF3]+ (100)
3d 8.83 (d, 2 H, H(4), H(6),
4JH,H = 1.9); 9.15 (t, 1 H,
–41.65 (s, CF3)
–41.62 (s, CF3)
268 [M]+ (100), 249 [M – F]+ (5), 222 [M – NO2]+ (5),
203 [M – F – NO2]+ (1), 175 [M – NO2 – HNO2]+ (15),
106 [M – NO2 – HNO2 – CF3]+ (20)
4
H(2), JH,H = 1.9)
3e 8.27 (s, H(4), H(6))
302 [M]+ (100), 283 [M – F]+ (5), 268 [M – Cl]+ (1),
256 [M – NO2]+ (2), 233 [M – CF3]+ (2),
210 [M – 2 NO2]+ (9), 141 [M – 2 NO2 – CF3]+ (16),
69 [CF3]+ (19)
3f
7.64 (d, 1 H, H(6), 3JH,H = 8.4);
7.80 (dd, 1 H, H(5), 4JH,H = 2.1,
3JH,H = 8.4); 8.16 (d, 1 H, H(3),
4JH,H = 2.1)
–42.52 (s, CF3)
–42.09 (s, CF3)
257 [M]+ (100), 238 [M – F]+ (4), 211 [M – NO2]+ (10),
188 [M – CF3]+ (7), 142 [M – NO2 – CF3]+ (53),
107 [M – CF3 – NO2 – Cl]+ (23), 69 [CF3]+ (32)
3g 7.40 (d, 1 H, Н(5), 3JH,H = 7.5);
7.48 (d, 1 H, Н(6), 3JH,H = 8.5);
7.75 (s, 1 H, Н(3))
246 [M]+ (100), 227 [M – F]+ (12), 177 [M – CF3]+ (84),
142 [M – CF3 – Cl]+ (93), 107 [M – CF3 – 2 Cl]+ (23),
69 [CF3]+ (48)
3h 7.64 (m, H(2), Н(3), H(5), Н(6))
–42.43 (s, CF3)
–42.54 (s, CF3)
256 [M]+ (57), 187 [M – CF3]+ (52),
108 [M – CF3 – Br]+ (100), 69 [CF3]+ (90)
223 [M]+ (100), 204 [M – F]+ (6), 177 [M – NO2]+ (26),
108 [M – NO2 – CF3]+ (74), 69 [CF3]+ (73)
3i
7.66 (t, 1 H, H(5), 3JH,H = 7.9);
8.00 (d, 1 H, H(4), 3JH,H = 7.2);
8.37 (dt, 1 H, H(6), 4JH,H = 1.0,
3JH,H = 8.2); 8.53 (t, 1 H, H(2),
4JH,H = 1.7)
3j
7.72 (d, 2 H, H(3), Н(5),
–41.00 (s, CF3)
223 [M]+ (92), 204 [M – F]+ (10), 193 [M – NO]+ (39),
177 [M – NO2]+ (9), 108 [M – NO2 – CF3]+ (69),
69 [CF3]+ (100)
291 [M]+ (100), 272 [M – F]+ (2), 245 [M – NO2]+ (5),
222 [M – CF3]+ (21), 172 [M – C2F5]+ (14),
126 [M – NO2 – C2F5]+ (42), 69 [CF3]+ (26)
3JH,H = 8.0); 8.19 (d, 2 H, H(2),
3
Н(6), JH,H = 8.0)
4a 7.42 (dd, 1 H, Н(6), 3JH,F = 7.5,
3JH,H = 9.0); 8.44 (m, 1 H, H(5));
8.58 (dd, 1 H, H(3), 4JH,F = 9.0,
4JH,H = 7.5)
–93.21 (m, 1 F,
F—Ar); –91.54 (dq,
2 F, SCF2,
3JCF ,CF3 = 3.0,
2
5JCF ,F = 1.6);
2
–83.30 (dt, 3 F, СF3,
3JCF ,CF3 = 3.0,
2
6JCF ,F = 1.6)
3
4b 7.78 (d, 1 H, H(6), 3JH,H = 8.0);
8.35 (d, 1 H, H(5), 3JH,H = 8.0);
8.60 (s, 1 H, Н(3))
–91.73 (s, 2 F,
SCF2); –82.14 (s,
3 F, CF3)
307 [M]+ (100), 291 [M – O]+ (2), 238 [M – CF3]+ (18),
226 [M – Cl – NO2]+ (7), 188 [M – C2F5]+ (21),
142 [M – C2F5 – NO2]+ (53), 119 [C2F5]+ (31),
107 [M – C2F5 – NO2 – Cl]+ (45), 69 [CF3]+ (65)
351 [M]+ (100), 282 [M – CF3]+ (10),
226 [M – NO2 – Br]+ (22), 186 [M – NO2 – C2F5]+ (16),
157 [M – NO2 – CF3 – Br]+ (16), 119 [C2F5]+ (16),
107 [M – C2F5 – NO2 – Br]+ (36)
4c 7.96 (d, 1 H, H(6), 3JH,H = 8.9);
8.20 (dd, 1 H, H(5), 3JH,H = 8.9,
4JH,H = 2.7); 8.62 (d, 1 H, Н(3),
4JH,H 2.4)
–91.29 (s, 2 F,
SCF2); –83.17 (t,
3 F, СF3,
3JCF ,CF2 = 3.4)
3
(to be continued)

428
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Table 5 (continued)
Comꢀ
pound
NMR (δ, J/Hz)
MS, m/z (Irel (%))
1H
19F
4d 8.83 (t, H(4), Н(6), 4JH,H = 2.0);
9.16 (t, H(2), 4JH,H = 2.0)
–90.94 (q,
2 F, SCF2,
318 [M]+ (100), 299 [M – F]+ (1), 272 [M – NO2]+ (2),
249 [M – CF3]+ (19), 225 [M – NO2 – HNO2]+ (17),
203 [M – NO2 – CF3]+ (2), 157 [M – 2 NO2 – CF3]+ (1),
153 [M – NO2 – C2F5]+ (1), 119 [C2F5]+ (8),
106 [M – NO2 – HNO2 – C2F5]+ (21),
3JCF ,CF3 = 3.3),
2
–82.53 (t, 3 F,
СF3, 3JCF ,CF2 = 3.4)
3
75 [M – 2 NO2 – SC2F5]+ (23)
4e 8.27 (s, H(4), H(6))
–90.88 (q, 2 F, SСF2,
352 [M]+ (100), 316 [M – Cl]+ (1), 283 [M – CF3]+ (6),
237 [M – CF3 – NO2]+ (2), 233 [M – C2F5]+ (4),
191 [M – CF3 – 2 NO2]+ (2), 187 [M – C2F5 – NO2]+ (1),
106 [M – 2 NO2 – C2F5 – Cl]+ (20)
307 [M]+ (100), 271 [M – Cl]+ (1), 188 [M – C2F5]+ (18),
142 [M – C2F5 – NO2]+ (60), 119 [C2F5]+ (8),
107 [M – C2F5 – NO2 – Cl]+ (26),
75 [M – SC2F5 – NO2 – Cl]+ (11), 69 [CF3]+ (27)
296 [M]+ (75), 177 [M – C2F5]+ (75),
142 [M – C2F5 – Cl]+ (100), 107 [M – C2F5 – 2 Cl]+ (30),
69 [CF3]+ (76)
3JCF ,CF3 = 3.3);
2
–82.74 (t, 3 F, СF3,
3JCF ,CF2 = 3.4)
–913.70 (s, 2 F,
SCF2); –82.88 (s,
3 F, CF3)
4f
7.66 (d, 1 H, H(6), 3JH,H = 8.4);
7.81 (dd, 1 H, Н(5), 3JH,H = 8.1,
4JH,H = 2.1); 8.17 (d, 1 H, H(3),
4JH,H = 2.1)
4g 7.46 (d, 2 H, Н(5), Н(6),
3JH,H = 8.2); 7.75 (s, 1 H, Н(3))
–91.58 (s, 2 F,
SCF2); –83.32 (s,
3 F, CF3)
4h 7.42 (m, H(2), Н(3), H(5), Н(6))
–90.45 (s, 2 F,
SCF2); –82.10 (s,
3 F, CF3)
306 [M]+ (91), 287 [M – F]+ (1), 237 [M – CF3]+ (2),
208 [M – Br – F]+ (17), 189 [M – C2F5]+ (68),
158 [M – CF3 – Br]+ (6), 119 [C2F5]+ (21),
108 [M – C2F5 – Br]+ (100), 69 [CF3]+ (47)
273 [M]+ (100), 254 [M – F]+ (1), 227 [M – NO2]+ (16),
157 [M – HNO2 – CF3]+ (6), 154 [M – C2F5]+ (9),
108 [M – NO2 – C2F5]+ (83), 69 [CF3]+ (58)
3
4i
4j
7.58 (t, 1 H, H(5), JH,H = 8.0);
–90.53 (s, 2 F,
SCF2); –82.44 (s,
3 F, CF3)
3
7.91 (d, 1 H, Н(4), JH,H = 8.0);
8.27 (d, 1 H, H(6), 3JH,H = 8.0);
8.45 (s, 1 H, Н(2))
7.27 (d, 2 H, H(3), Н(5),
3JH,H = 8.0); 8.18 (d, 2 H,
H(2), Н(6), JH,H = 8.0)
–91.58 (s, 2 F,
SCF2); –82.19 (s,
3 F, CF3)
273 [M]+ (100), 254 [M – F]+ (2), 243 [M – NO]+ (35),
227 [M – NO2]+ (5), 207 [M – HNO2 – F]+ (14),
157 [M – CF3 – HNO2]+ (9), 124 [M – NO – C2F5]+
(19), 108 [M – C2F5 – NO2]+ (84), 69 [CF3]+ (80)
323 [M]+ (92), 305 [M – F]+ (1), 255 [M – CF3]+ (12),
226 [M – F – Br]+ (17), 205 [M – C2F5]+ (33),
176 [M – CF3 – Br]+ (14), 126 [M – C2F5 – Br]+ (100),
69 [CF3]+ (35)
3
4k 7.10 (dd, 1 H, H(6),
3JH,H = 8.8, 3JH,F = 8.0);
7.63 (m, 1 H, H(5));
–106.35 (m, 1 F,
F—Ar); –91.88 (m,
2 F, SCF2);
7.79 (dd, 1 H, H(3),
4JH,F = 6.1, 4JH,H = 2.5)
–83.33 (dt, СF3,
3JCF ,CF2 = 3.3,
3
6JCF ,F = 1.4)
3
5a 7.42 (dd, 1 H, H(6),
3JH,H = 9.2, 3JH,F = 7.5);
8.45 (m, 1 H, H(5));
–124.16 (br.s, 2 F, CF2);
–92.95 (m, 1 F, F—Ar);
–87.29 (m, 2 F, SCF2);
–80.52 (t, 3 F, СF3,
341 [M]+ (100), 322 [M – F]+ (5), 295 [M – NO2]+ (2),
276 [M – F – NO2]+ (3), 222 [M – C2F5]+ (43),
172 [M – C3F7]+ (18), 126 [M – C3F7 – NO2]+ (46),
94 [M – SC3F7 – NO2]+ (10), 69 [CF3]+ (33)
8.60 (dd, 1 H, H(3),
4JH,F = 5.8, 4JH,H = 2.7)
5b 7.78 (d, 1 H, H(6), 3JH,H
8.0); 8.30 (d, 1 H, H(5),
3JH,H = 8.0);
3JCF ,CF2 = 9.3)
3
=
–123.48 (s, 2 F,
SCF2CF2CF3);
–86.32 (s, 2 F, SCF2);
–79.70 (s, 3 F, CF3)
–124.21 (s, 2 F,
SCF2CF2CF3);
–87.06 (m, 2 F, SCF2);
–80.65 (s, 3 F, CF3)
357 [M]+ (100), 311 [M – NO2]+ (2), 292 [M – NO2 – F]+
(2), 276 [M – NO2 – Cl]+ (3), 238 [M – C2F5]+ (39),
182 [M – C3F7]+ (19), 142 [M – C3F7 – NO2]+ (31),
107 [M – C3F7 – NO2 – Cl]+ (25), 69 [CF3]+ (40)
401 [M]+ (84), 385 [M – O]+ (2), 282 [M – C2F5]+ (30),
232 [M – C3F7]+ (16), 203 [M – C2F5 – Br]+ (12),
186 [M – C3F7 – NO2]+ (26),
8.63 (s, 1 H, Н(3))
5c 7.96 (d, 1 H, H(6),
3JH,H = 8.9); 8.21 (dd, 1 H,
3
H(5), JH,H = 8.9,
4JH,H = 2.7); 8.62 (d, 1 H,
157 [M – C2F5 – NO2 – Br]+ (33),
107 [M – C3F7 – NO2 – Br]+ (74), 69 [CF3]+ (100)
4
H(3), JH,H = 2.7)
(to be continued)

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
429
Table 5 (continued)
Comꢀ
pound
NMR (δ, J/Hz)
MS, m/z (Irel (%))
1H
19F
5d 8.83 (s, 2 H, Н(4), Н(6),
4JH,H = 2.0); 9.19 (t, 1 H,
–123.68 (br.s, 2 F,
SCF2CF2CF3);
368 [M]+ (100), 349 [M – F]+ (19), 333 [M – F – O]+
(15), 299 [M – CF3]+ (11), 275 [M – NO2 – HNO2]+
(43), 249 [M – C2F5]+ (96), 233 [M – C2F5 – O]+ (9),
199 [M – C3F7]+ (28), 183 [M – C3F7 – O]+ (9),
169 [C3F7]+ (45), 153 [M – C3F7 – NO2]+ (15),
119 [C2F5]+ (18)
4
Н(2), JH,H = 2.0)
–86.87 (t, 2 F, SCF2,
3JS,CF ,CF2 = 9.0);
–80.452(t, 3 F, CF3,
3JCF ,CF2 = 9.0)
3
5e 7.10 (dd, 1 H, H(6),
3JH,H = 8.7, 3JH,F = 8.1);
7.63 (m, 1 H, H(5));
–124.25 (br.s, 2 F,
SCF2CF2CF3);
374 [M]+ (100), 355 [M – F]+ (2), 295 [M – Br]+ (1),
276 [M – F – Br]+ (24), 255 [M – C2F5]+ (32),
205 [M – C3F7]+ (36), 176 [M – C2F5 – Br]+ (34),
126 [M – C3F7 – Br]+ (92), 94 [M – SC3F7 – Br]+ (12),
69 [CF3]+ (31)
–106.07 (m, 1 F, F—Ar);
–87.53 (m, 2 F, SCF2);
–80.60 (dt, 3 F,
7.80 (dd, 1 H, H(3),
4JH,F = 6.1, 4JH,H = 2.5)
СF3, 3JCF ,CF2 = 9.0,
3
4JCF ,CF2 = 0.8)
3
11a 7.70 (d, H(6), 3JH,F = 7.9);
8.31 (d, H(3), 4JH,F = 5.9)
–93.60 (m, 1 F, F—Ar);
–61.04 (s, 3 F, CF3);
–41.04 (d, 3 F, SCF3,
309 [M]+ (100), 290 [M – F]+ (15), 263 [M – NO2]+ (10),
194 [M – NO2 – CF3]+ (93), 175 [M – F – NO2 – CF3]+
(10), 106 [M – NO2 – F – 2CF3]+ (3), 69 [CF3]+ (33)
5JS,CF ,F = 5.2)
3
11b 7.90 (s, H(6)); 8.20 (s, H(3))
11c 8.16 (s, Н(6)); 8.24 (s, Н(3))
–60.86 (s, ArCF3);
–40.78 (s, SCF3)
325 [M]+ (100), 306 [M – F]+ (14), 279 [M – NO2]+ (11),
244 [M – Cl – NO2]+ (7), 210 [M – NO2 – CF3]+ (32),
175 [M – CF3 – NO2 – Cl]+ (44),
143 [M – Cl – NO2 – SCF3]+ (5),
106 [M – 2 CF3 – NO2 – Cl]+ (14), 69 [CF3]+ (27)
369 [M]+ (89), 350 [M – F]+ (11), 323 [M – NO2]+ (8),
254 [M – NO2 – CF3]+ (58), 244 [M – NO2 – Br]+ (14),
175 [M – NO2 – CF3 – Br]+ (100),
–60.73 (s, ArCF3);
–40.86 (s, SCF3)
143 [M – NO2 – SCF3 – Br]+ (12),
106 [M – NO2 – 2 CF3 – Br]+ (49), 69 [CF3]+ (91)
336 [M]+ (100), 317 [M – F]+ (18), 290 [M – NO2]+ (1),
271 [M – F – NO2]+ (2), 244 [M – 2 NO2]+ (4),
143 [M – 2 NO2 – SCF3]+ (25),
11d 8.16 (s, H(4), H(6))
–56.96 (s, ArCF3);
–39.94 (s, SCF3)
106 [M – 2 CF3 – 2 NO2]+ (16), 69 [CF3]+ (45)
314 [M]+ (100), 295 [M – F]+ (18), 279 [M – Cl]+ (1),
245 [M – CF3]+ (33), 226 [M – CF3 – F]+ (5),
211 [M – CF3 – Cl]+ (38), 175 [M – CF3 – 2 Cl]+ (11),
106 [M – 2 CF3 – 2 Cl]+ (4), 69 [CF3]+ (18)
414 [M]+ (65), 345 [M – CF3]+ (100),
11e 7.63 (s, Н(6)); 7.84 (s, Н(3))
12a 7.64 (s, Н(6)); 7.92 (s, Н(3))
–63.82 (s, ArCF3);
–41.20 (s, SCF3)
–112.42 (s, ArCF2);
–90.85 (s, SCF2);
–83.77, –83.64
226 [M – CF3 – C2F5]+ (62),
191 [M – CF3 – C2F5 – Cl]+ (50), 69 [CF3]+ (45)
(both s, 3 F each, CF3)
–109.47 (s, ArCF2);
–89.94 (s, SCF2);
–82.40, –82.06
(both s, 3 F each, CF3)
–112.00 (br.s, 2 F,
ArCF2); –103.85 (m,
F—Ar); –91.00 (s,
2 F, SCF2);
12b 7.84 (d, 1 H, Н(4), 3JH,H
8.0); 8.03 (s, 1 H, Н(6));
8.06 (d, 1 H, Н(3),
=
391 [M]+ (72), 322 [M – CF3]+ (42),
226 [M – C2F5 – NO2]+ (17),
157 [M – C2F5 – CF3 – NO2]+ (38), 119 [C2F5]+ (26),
69 [CF3]+ (66)
3JH,H = 8.0)
12c 7.49 (d, H(6), 3JH,F = 8.5);
8.07 (d, Н(3), 4JH,F = 6.3)
442 [M]+ (91), 423 [M – F]+ (6), 373 [M – CF3]+ (100),
344 [M – F – Br]+ (22), 275 [M – F – Br – CF3]+ (4),
254 [M – C2F5 – CF3]+ (51),
175 [M – C2F5 – CF3 – Br]+ (66), 119 [C2F5]+ (24),
69 [CF3]+ (53)
–83.37, –83.02
(both s, 3 F each, CF3)
(to be continued)

430
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Table 5 (continued)
Comꢀ
pound
NMR (δ, J/Hz)
MS, m/z (Irel (%))
1H
19F
13 7.47 (d, H(6), 3JH,F = 8.5);
8.05 (d, H(3), 4JH,F = 6.3)
–124.43, –124.14
(both br.s, 2 F each, CF2);
–108.77 (m, 2 F, ArCF2);
–103.77 (t, 1 F, F—Ar,
5JF,CF2 = 6.4);
542 [M]+ (61), 523 [M – F]+ (10), 423 [M – C2F5]+ (90),
375 [M – C3F7]+ (16), 344 [ M – C2F5 – Br]+ (15),
294 [M – C3F7 – Br]+ (23), 254 [M – C3F7 – C2F5]+ (76),
175 [M – C3F7 – C2F5 – Br]+ (100),
143 [M – SC3F7 – C2F5 – Br]+ (20), 119 [C2F5]+ (19),
69 [CF3]+ (52)
–86.71 (m, 2 F, SCF2);
–80.54 (t, 3 F, СF3,
3JCF ,CF2 = 10.0);
–80.439 (t, 3 F, СF3,
3JCF ,CF2 = 9.3)
3
14a 8.60 (d, H(6), 4JH,H = 2.6);
8.80 (d, H(4), 4JH,H = 2.6)
–63.98 (s, ArCF3);
–41.29 (s, SCF3)
325 [M]+ (100), 306 [M – F]+ (11), 279 [M – NO2]+ (13),
244 [M – Cl – NO2]+ (7), 210 [M – NO2 – CF3]+ (87),
175 [M – Cl – CF3 – NO2]+ (42),
143 [M – Cl – SCF3 – NO2]+ (9),
106 [M – 2 CF3 – NO2 – Cl]+ (14), 69 [CF3]+ (49)
369 [M]+ (78), 254 [M – NO2 – CF3]+ (23),
14b 8.62 (s, Н(6));
–63.91 (s, ArCF3);
–41.38 (s, SCF3)
8.78 (s, Н(4))
244 [M – NO2 – Br]+ (49), 175 [M – NO2 – CF3 – Br]+
(79), 106 [M – NO2 – 2 CF3 – Br]+ (4), 69 [CF3]+ (100)
This equation shows that the higher the charge on the
sulfur atom and the more positive the charge on the H(4)
atom, which is observed when electronꢀwithdrawing subꢀ
stituents are introduced into the benzene ring, the higher
the yield of the target product.
lated, most likely, to steric effects for the addition of
relatively bulky pentafluoroethyl and pentafluoropropyl
radicals,10 whereas the reactions involving the trifluoroꢀ
methyl radical are predominantly determined by the enꢀ
ergy of electronic structure rearrangement and are charꢀ
LUMO
These differences in perfluoroalkylation reactions deꢀ
pending on the size of the perfluoroalkyl radical are reꢀ
acterized by ЕβHOMO and Еβ
.
Thus, the method proposed for the formation of aryl
perfluoroalkyl sulfides from aromatic disulfides can be of
preparative value for compounds containing several elecꢀ
tronꢀwithdrawing substituents in the aromatic ring. This
method was used for the first time to synthesize comꢀ
pounds 3e and 4e, which can be used as starting comꢀ
pounds in the synthesis of a series of new amino derivaꢀ
tives. The presence of a fluorineꢀcontaining electronꢀwithꢀ
drawing substituent along with two nitro groups in the
benzene ring increases the chlorine atom mobility in molꢀ
ecules of compounds 3e and 4e. These compounds react
readily with secondary amines at room temperature, which
results in a series of analogs of the known herbicides based
on 4ꢀaminoꢀ2,6ꢀdinitrobenzotrifluoride3 in high yields
(Scheme 5).
Scheme 5
In compounds 3—5d, one and two nitro groups were
reduced to afford amino (24) and diamino derivatives
(25a—c), respectively. One nitro group was selectively
reduced with hydrazine hydrate on refluxing in ethanol.
The diamines were prepared by the action of iron in the
presence of HCl (Scheme 6).
Compounds 25a—c can find use as monomers in the
synthesis of such an important class of modern materials
as fluorineꢀcontaining polyimides.11
22
R1
R2
23: n = 1 (a), 2 (b)
a
b
c
Et
Pr
Et
Bu
cyclopropylmethyl
methallyl

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
431
Table 6. Data on the 13С NMR spectra and highꢀresolution mass spectra of compounds 3a,b,d—g, 4a,c,d—g,k, 5a,d,e, and 6a
Comꢀ
pound
13С NMR (δ, J/Hz)
Highꢀresolution mass spectrum
Found,
Molecular
formula
Calculaꢀ
ted, M
m/z [M]+
3a
3b
114.0 (dq, C(2), 2JCF = 20.8, 3JCCF = 2.6); 117.6 (d, C(6), 2JCF = 25.4);
240.9827
256.9533
C7H3F4NO2S
240.9821
3
4
128.5 (qd, CF3, JCF = 310.0, JCF = 1.6); 129.7 (d, C(5), 3JCF = 10.2);
134.1 (s, С(3)); 144.3 (s, С(4)); 166.7 (d, C(1), JCF = 263.3)
3
126.4 (q, C(2), JCCF = 2.4); 126.7 (s, С(6)); 128.5 (q, CF3, JCF = 310.1);
C7H3ClF3NO2S
256.9525
3
131.4 (s, С(5)); 132.3 (q, C(3), 4JCF = 1.1); 139.8 (s, С(1)); 146.5 (q, C(4),
5JCF = 0.9)
120.9 (s, С(2)); 128.5 (q, СF3, JCF = 309.7); 129.3 (q, C(5), 3JCCF3 = 2.5);
3d
3e
3f
267.9766
301.9367
256.9521
C7H3F3N2O4S
C7H2ClF3N2O4S
C7H3ClF3NO2S
267.9766
301.9376
256.9525
4
135.3 (q, C(4), C(6), JCCF = 1.1); 148.7 (br.s, С(1), С(3))
3
3
123.6 (s, С(2)); 126.6 (q, C(5), JCCF = 2.7); 128.3 (q, CF3, JCF = 310.1);
134.2 (q, C(4), C(6), JCCF = 1.1); 1349.8 (s, С(1), С(3))
4
3
3
124.8 (q, С(4), JCCF = 2.5); 128.8 (q, CF3, JCF = 309.1); 130.4 (s, С(1));
3
4
132.6 (q, C(5), JCCF = 1.0); 133.0 (s, С(6)); 140.2 (q, C(3), 4JCCF3 = 0.9);
3
148.1 (br.s, С(2))
—
3g
4a
245.9258
290.9792
C7H3Cl2F3S
C8H3F6NO2S
245.9285
290.9789
3
112.5 (dt, C(2), 2JCF = 21.4, JCCF = 3.4); 117.5 (d, C(6), 2JCF = 25.8);
3
118.4 (qt, CF2, JCF = 286.9, 2JCF = 36.2); 119.5 (tqd, CF3, JCF = 282.9,
2JCF = 41.4, 5JCF = 1.2); 129.6 (d, C(5), 3JCF = 10.2); 134.9 (s, C(3));
144.3 (d, C(4), 4JCF = 2.9); 167.3 (d, C(1), JCF = 263.3)
—
4c
4d
352.8946
317.9752
C8H3BrF5NO2S
C8H3F5N2O4S
352.8968
317.9734
118.3 (qt, CF2, JCF = 286.6, 2JCF = 35.8); 119.3 (tq, CF3, JCF = 292.4,
3
2JCF = 41.6); 121.3 (s, С(2)); 127.8 (t, C(5), JCCF3 = 3.2); 136.3 (s, С(4),
C(6)); 148.7 (br.s, С(3), С(1))
—
4e
4f
351.9336
306.9486
C8H2ClF5N2O4S
C8H3ClF5NO2S
351.9343
306.9493
2
118.4 (qt, CF2, JCF = 286.6, JCCF = 36.2); 119.7 (tq, CF3,
3
JCF = 290.9, 2JCF = 41.1); 123.3 (t, С(4), JCCF3 = 3.0); 130.7 (s, С(1));
3
132.9 (s, С(6)); 133.4 (s, С(5)); 141.0 (s, С(3)); 148.1 (m, С(2))
—
4g
4k
295.9222
323.9038
C8H3Cl2F5S
C8H3BrF6S
295.9253
323.9043
3
112.2 (dt, С(2), 3JCCF = 2.9, JCF = 20.0); 116.8 (q, C(4), 4JCF = 4.1);
118.2 (q, C(6), JCF =324.5); 118.4 (qt, CF2, JCF = 286.5, JCF = 36.5);
2
2
2
119.6 (tq, CF3, JCF = 291.6, JCF = 41.0); 137.0 (q, C(5), 3JCF = 8.2);
141.5 (s, C(3)); 163.0 (d, C(1), JCF = 253.6)
5a
5d
5e
—
—
340.9728
367.9710
373.9008
C9H3F8NO2S
C9H3F7N2O4S
C9H3BrF8S
340.9757
367.9702
373.9011
2
2
109.3 (tm, CF2, JCF = 267.1, JCF = 38.5); 112.8 (qt, С(2), JCF = 19.8,
3JCCF = 3.2); 117.4 (d, C(4), 4JCF = 4.1); 118.3 (qm, CF3, JCF = 290.7,
3
2JCF = 32.4, JCF = 1.6); 118.7 (d, C(6), 2JCF = 24.5); 122.6 (t.t, SCF2,
3
JCF = 293.4, 2JCF = 34.0); 137.6 (d, C(5), JCF = 8.2); 142.4 (s, C(3));
3
164.0 (d, C(1), JCF = 253.6)
6a
117.0 (dq, C(6), 2JCF = 28.4, 3JCCF = 5.5); 118.5 (d, C(2), 2JCF = 20.2);
341.8947
C8H2BrF7S
341.8948
3
120.7 (q, CF3, JCF = 274.5); 128.2 (q, SCF3, JCF = 309.9); 129.1 (dq, C(5),
2JCCF = 35.8, 3JCF = 8.7); 134.8 (s, С(3)); 144.1 (s, С(4)); 164.2 (d, C(1),
JCF =3262.9)

432
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
Sipyagin et al.
Table 7. Wavefunction coefficients of the sulfur
atom (СS) in radicals 18e,f,h,j and yields of comꢀ
pounds ArSRF (RF = CF3 (3e,f,h,j), and C2F5
(4e,f,h,j))
CFCl3 as internal standards. IR spectra were obtained on BioRad
FTSꢀ40 FTꢀIR and Specord Mꢀ80 instruments in Nujol. GCꢀMS
analysis was carried out on a Hewlett—Packard 5890 GCꢀmass
spectrometer (70 eV) using a capillary column (30 m) with
HP1 oil. Highꢀresolution mass spectra were recorded on a
VG Autospec mass spectrometer.
Intermeꢀ
CS
Yield (%))
diate 18
Synthesis of disulfides 2a—n (general procedure). Areneꢀ
sulfonyl chloride (0.25 mol) was dissolved in glacial AcOH
(1.25 L) saturated with gaseous HBr (125 g). Phenol (25.9 g,
0.275 mol) was added, and the reaction mixture was slowly
heated with stirring to 55—60 °С (exothermic reaction). The
reaction mixture was stirred at this temperature for 24—36 h,
cooled to ≈20 °C, and diluted with water. The precipitate that
formed was filtered off, washed with water, dried in air, and
recrystallized from EtOH or AcOH. The yields of the resulting
3
4
e
f
h
j
0.032
0.801
0.489
0.799
73.0
16.1
24.6
15.2
66.4
16.9
34.1
30.3
Scheme 6
1
compounds, melting points, and data on the Н and 13С NMR
and mass spectra are presented in Tables 1 and 2.
Reactions of disulfides 2a—n with perfluoroalkyl radicals (genꢀ
eral procedure). Method A. A disulfide 2 (2.7 mmol) was added
with stirring at –20 °С to a mixture of XeF2 (1.4 g, 8.2 mmol),
perfluoroalkanecarboxylic acid (1.2—1.8 mL), and CH2Cl2
(30 mL). The mixture spontaneously warmed to +5 °С.
Method B. XeF2 (1.4 g, 8.2 mmol) was added at 30 °С with
stirring to a mixture of the starting disulfide (2.74 mmol) in
perfluoroalkanecarboxylic acid (4.2—6.0 mL, 54.8 mmol). In
both cases, the end of the reaction was determined by the end of
gas liberation.
The reaction mixture obtained by methods A or B was neuꢀ
tralized with a solution of Na2CO3, extracted with chloroform,
and dried with Na2SO4. The solvent was removed in vacuo. The
residue was chromatographed on silica gel (light petroleum (3g,h,
4g,h,k, 5e, 6e, 7a,c, and 8) or a benzene—heptane (1 : 2) mixꢀ
ture (3a—f,i,j, 4a—f,i,j, 5a—d, 6a—d, 7b, and 9a,b) as eluents).
The yields of the synthesized compounds, melting points, and
data on the 1Н, 13С, and 19F NMR and mass spectra are preꢀ
sented in Tables 3, 7, and 8.
25: n = 1 (a), 2 (b), 3 (c)
3ꢀNitroꢀ5ꢀ(trifluoromethylthio)aniline (24). A mixture of
1,3ꢀdinitroꢀ5ꢀ(trifluoromethylthio)benzene (0.31 g, 1.16 mmol)
and hydrazine hydrate (0.25 g, 5.00 mmol) in EtOH (20 mL)
was refluxed for 6 h. The solvent was distilled off, and the resiꢀ
due was washed with water (50 mL) and dissolved in benzene.
The solution was dried with Na2SO4 and concentrated in vacuo.
After recrystallization from hexane, compound 24 (0.1 g, 36.2%)
was obtained as orange crystals, m.p. 118—120 °С (Ref. 18:
Experimental
Column chromatography was carried out on silica gel 60,
230—400 mesh (Merck), and TLC was performed on plates with
silica gel 60 F254 (Merck). NMR spectra were recorded on Bruker
AM 360 or Bruker AM 500 spectrometers with working frequenꢀ
cies of 360 and 500 MHz, respectively, in CDCl3 using Me4Si or
Table 8. Quantum characteristics of radicals 18a—d,g,i,k and yields of compounds ArSRF (RF
CF3 (3а—d,g,i), C2F5 (4a—d,g,i,k), and C3F7 (5a—c,k))
=
HOMO
LUMO
Interꢀ
mediate
18
QS
–QCS
QH
QH4
–Еβ
Еβ
Yield (%)
a.u.
eV
3
4
5
a
b
c
d
g
i
0.1464
0.1569
0.1525
0.1352
0.1507
0.1307
0.1352
0.1331
0.1111
0.1189
0.1143
0.1129
0.1182
0.1348
0.0955
0.0993
0.0969
0.1026
0.0861
0.0923
0.0789
0.0773
0.0813
0.0796
0.1038
0.0804
0.0773
—
6.9863
4.8944
4.6753
6.6864
4.5395
5.8697
5.0562
—
33.6
24.5
34.7
30.0
22.5
7.8
55.3
37.7
40.2
14.7
13.3
8.1
33.0
26.7
27.3
—
—
—
7.1076
7.6223
7.3029
6.9044
6.8079
—
k
—
23.0
16.7

Perfluoroalkylation of aromatic disulfides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
433
117—121 °С). 1H NMR, δ: 4.21 (s, 2 H, NH2); 7.21 (s, 1 H,
1.28, 1.57 (both m, 2 H each, CH2); 2.98 (t, 2 H, CH2, J =
7.2 Hz); 3.10 (q, 2 H, CH2N, J = 6.1 Hz); 8.07 (s, 2 H, Ar).
19F NMR, δ: –41.90 (s). MS, m/z (Irel (%)): 367 [M]+ (2), 350
[M – OH]+ (6), 324 [M – C3H7]+ (100), 308 [M – C3H7O]+
(11), 296 [M – C3H7 – C2H4]+ (25). Found: m/z 367.082 [M]+.
C13H16F3N3O4S. Calculated: M = 367.081.
4
Н(4)); 7.58 (t, 1 H, H(2), JH,H = 2.0 Hz); 7.83 (s, 1 H, Н(6)).
13С NMR, δ: 111.1 (s, С(2)); 119.6 (q, C(6), JCCF = 0.9 Hz);
4
126.7 (q, С(4), JCCF = 0.9 Hz); 126.8 (q, С(53), JCCF
=
4
3
3
3
2.3 Hz); 129.2 (q, CF3, JCF = 303.6 Hz); 148.1 (s, С(3)); 149.4
(s, С(1)). 19F NMR, δ: –42.49 (s, CF3). IR, ν/cm–1: 3420
(NH2). MS, m/z (Irel (%)): 238 [M]+ (100), 222 [M – F]+ (1),
192 [M – NO2]+ (19), 123 [M – NO2 – CF3]+ (41). Found:
m/z 238.0022 [M]+. C7H5F3N2O2S. Calculated: M = 238.0024.
Reduction of 1,3ꢀdinitroꢀ4ꢀperfluoroalkylthiobenzenes (3d,
4d, and 5d) (general procedure). An Fe powder (4—5 mmoles per
NO2 group) was added portionwise with stirring to a boiling
solution of a nitro compound in ethanol (5 mL) containing
concentrated HCl (0.2 mL). The mixture was refluxed for 8 h
until the nitro compound disappeared completely (TLC) and
then refluxed with active carbon, filtered, cooled to ≈20 °С, and
neutralized with aqueous NH4OH. The solvent was removed
in vacuo and extracted with benzene. The organic layer was
dried with Na2SO4. The solvent was removed, and the product
was purified by column chromatography and recrystallization
from hexane. Vacuum sublimation was carried out for complete
purification.
NꢀCyclopropylmethylꢀNꢀpropylꢀ2,6ꢀdinitroꢀ4ꢀtrifluoroꢀ
methylthioaniline (22b). The yield was 82%, yellowishꢀorange
crystals, m.p. 54—55 °C. 1H NMR, δ: 0.16, 0.58 (both m,
2 H each, CH2); 0.88 (t, 3 H, CH3, J = 7.5 Hz); 1.59 (m, 3 H,
CH, CH2); 2.90 (d, 2 H, CH2, J = 6.8 Hz); 3.09 (m, 2 H,
CH2N); 8.21 (s, 2 H, Ar). 19F NMR, δ : –41.87 (s). MS,
m/z (Irel (%)): 379 [M]+ (7), 362 [M – OH]+F(24), 350 [M – Et]+
(51), 334 [M – OEt]+ (3), 296 [M – Et – С4Н6]+ (5). Found:
m/z 379.079 [M]+. C14H16F3N3O4S. Calculated: M = 379.081.
NꢀEthylꢀNꢀmethallylꢀ2,6ꢀdinitroꢀ4ꢀtrifluoromethylthioaniline
(22c). The yield was 84%, yellow crystals, m.p. 76—77 °C.
1H NMR, δ: 1.17 (t, 3 H, CH3, J = 7.2 Hz); 1.73 (s, 3 H, CH3);
3.10 (q, 2 H, CH2, J = 7.0 Hz); 3.53, 5.00 (both s, 2 H each,
CH2); 8.19 (s, 2 H, Ar). 19F NMR, δ: –41.76 (s). MS,
m/z (Irel (%)): 365 [M]+ (20), 348 [M – OH]+ (72), 324
[M – Allyl]+ (28), 308 [M – AllylO]+ (45), 296 [M – Allyl –
C2H4]+ (6).
2,6ꢀDinitroꢀ4ꢀ(trifluoromethylthio)ꢀ1ꢀpiperazinobenzene
(23a). The yield was 84%, yellowꢀred crystals, m.p. 114—115 °C.
1H NMR, δ: 1.72 (s, 1 H, NH); 2.96, 3.07 (both br.s, 4 H each,
CH2); 8.02 (s, 2 H, Ar). 19F NMR, δ: –42.95 (s). MS,
m/z (Irel (%)): 352 [M]+ (11), 322 [M – NO]+ (18), 310 [M –
C3H6]+ (11), 280 [M – NO – C3H6]+ (51), 259 [M – NO –
C4H8NH]+ (17), 246 (7), 218 (10). Found: m/z 352.044 [M]+.
5ꢀTrifluoromethylthioꢀ1,3ꢀphenylenediamine (25a). The yield
was 65.1%, yellowish crystals, m.p. 110—112 °С. 1H NMR, δ:
3.67 (s, 4 Н, NH2); 6.06 (d, 1 Н, H(2), 4JH,H = 1.9 Hz); 6.36 (d,
2 Н, H(4), H(6), 4JH,H = 1.7 Hz). 13С NMR, δ: 103.4 (s, С(2));
112.8 (q, C(4), C(6), 4JCCF = 0.5 Hz); 125.6 (q, C(5), 3JCCF
=
3
2.1 Hz); 129.8 (q, CF3, JCF3 = 307.8 Hz); 148.1 (s, С(1), С(3)).
19F NMR, δ: –42.85 с (CF3). IR, ν/cm–1: 3348 (NH2). MS,
m/z (Irel (%)): 208 [M]+ (100), 189 [M – F]+ (4), 139 [M – CF3]
(16), 122 [M – CF3 – NH3]+ (4), 69 [CF3]+ (10). Found:
m/z 208.0260 [M]+. C7H7F3N2S. Calculated: M = 208.0282.
5ꢀPentafluoroethylthioꢀ1,3ꢀphenylenediamine (25b). The
yield was 68.2%, yellowish crystals, m.p. 103—105 °С. 1H NMR,
C
11H11F3N4O4S. Calculated: M = 352.046.
2,6ꢀDinitroꢀ1ꢀpiperazinoꢀ4ꢀ(pentafluoroethylthio)benzene
(23b). The yield was 83%, yellow crystals, m.p. 55—57 °C.
1H NMR, δ: 2.27 (s, 1 H, NH); 2.98, 3.09 (both q, 4 H each,
2 CH2, J = 5.17 Hz); 8.03 (s, 2 H, Ar). 19F NMR, δ: –82.81 (s,
3 F, CF3); –91.99 (s, 2 F, CF2). MS, m/z (Irel (%)): 402 [M]+
(11), 372 [M – NO]+ (26), 360 [M – C3H6]+ (10), 330 [M –
NO – C3H6]+ (46), 309 [M – NO – C4H8NH]+ (12), 283 (11).
Found: m/z 402.043. C12H11F5N4O4S. Calculated: M = 402.042.
4
δ: 3.40 (s, 4 H, NH2); 6.09 (t, 1 H, H(4), JH,H = 1.7 Hz); 6.38
4
(d, 2 H, H(2), H(6), JH,H = 1.7 Hz). 19F NMR, δ: –91.96
(s, CF2); –83.01 (s, CF3). IR, ν/cm–1: 3350 (NH2). MS,
m/z (Irel (%)): 258 [M]+ (100), 139 [M – C2F5]+ (9). Found:
m/z 258.0248 [M]+. C8H7F5N2S. Calculated: M = 258.0250.
5ꢀHeptafluoropropylthioꢀ1,3ꢀphenylenediamine (25c). The
1
yield was 57.2%, yellowish crystals, m.p. 82—84 °С. H NMR,
References
4
δ: 3.52 (s, 4 H, NH2); 6.07 (t, 1 H, H(4), JH,H = 1.7 Hz); 6.37
4
(d, 2 H, H(2), H(6), JH,H = 1.7 Hz). 19F NMR, δ: –124.32
(s, CF2); –87.46 (s, SCF2); –80.45 (s, CF3). IR, ν/cm–1: 3352
(NH2). MS, m/z (Irel (%)): 308 [M]+ (100), 289 [M – F]+ (4),
239 [M – CF3]+ (16), 69 [CF3]+ (10). Found: m/z 308.0218
[M]+. C9H7F7N2S. Calculated: M = 308.0215.
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Reactions of secondary amines with chloroꢀ2,6ꢀdinitroꢀ4ꢀ
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ing amine (2.5 equiv.) was added with stirring to a solution of
chloroꢀ2,6ꢀdinitroꢀ4ꢀperfluoroalkylthiobenzene (1.5 mmol) in
MeOH or EtOH (10 mL). The mixture was refluxed for 30 min.
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eluent) (compounds 22a—c) or by recrystallization from EtOH
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NꢀButylꢀNꢀethylꢀ2,6ꢀdinitroꢀ4ꢀtrifluoromethylthioaniline
(22a). The yield was 84%, orangeꢀred crystals, m.p. 56—58 °C.
1H NMR, δ: 0.88, 1.18 (both t, 3 H each, CH3, J = 7.2 Hz);

434
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 2, February, 2004
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Received July 29, 2003;
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in revised form December 15, 2003