Synthesis and thiocyanation of N-Alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone monoimines

Article abstract of DOI:10.1134/S1070428011040075

New N-alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone monoimines were synthesized, and their thiocyanation gave 5-alkyl(trifluoromethyl)sulfonylamino- 1,3-benzoxathiol-2-ones. An intermediate thiocyanation product, 5-trifluoromethylsulfonylamino-1,3-benzo

Full text of DOI:10.1134/S1070428011040075

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 4, pp. 510–519. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, O.N. Mikhailichenko, S.V. Shelyazhenko, V.V. Pirozhenko, L.M. Yagupol’skii, 2011, published in
Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 4, pp. 513–522.
Synthesis and Thiocyanation of N-Alkyl(trifluoromethyl)sulfonyl
1,4-Benzoquinone Monoimines
A. P. Avdeenkoa, S. A. Konovalovaa, O. N. Mikhailichenkoa, S. V. Shelyazhenkob,
V. V. Pirozhenkob, and L. M. Yagupol’skii†b
a Donbass State Machine-Building Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
Received November 15, 2010
Abstract—New N-alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone monoimines were synthesized, and their
thiocyanation gave 5-alkyl(trifluoromethyl)sulfonylamino-1,3-benzoxathiol-2-ones. An intermediate thiocyana-
tion product, 5-trifluoromethylsulfonylamino-1,3-benzoxathiol-2-imine, was isolated for the first time.
DOI: 10.1134/S1070428011040075
N-Substituted p-quinone imines were reported for
the first time more than hundred years ago. Their
N-aryl [1, 2], N-acyl [3], N-arylsulfonyl [4–7], N-aryl-
sulfanyl [8], N-arylsulfinyl [9], N-(N-arylsulfonyl-
benzimidoyl) [10], and N-arylaminocarbonyl deriva-
tives [11] were synthesized and used for the prepara-
tion of various compounds possessing fungicidal, bac-
tericidal [12], and anticancer activity [13], as well as of
vulcanizing agents for rubber [14], corrosion inhibitors
[15], and powerful dehydrating agents [16]. On the
other hand, organic compounds with fluorine-contain-
ing substituents also find increasing application as
medicines, pesticides, dyes, and monomers for heat-
resistant polymers [17].
The reactivity of N-arylsulfonyl 1,4-benzoquinone
monoimines was studied in sufficient detail. Their
reactions with potassium thiocyanate [18–20], sodium
arenesulfinates [7, 21, 22], sodium azide [7, 23],
hydrogen halides [4, 24], halogens [25], aromatic
amines [7, 26], phenols and naphthols [5, 27], dialkyl
[7, 28, 29] and trialkyl phosphites [29, 30], aryl- and
acylhydrazines [31], and alcohols [6, 7, 22, 32] were
studied. It was found that the size and electron-with-
drawing power of the substituent on the nitrogen atom
strongly affect the reactivity of N-substituted p-qui-
none imines [18–22].
quinone monoimines, N-methylsulfonyl-1,4-benzo-
quinone monoimine, whose reactivity was not studied.
We previously presumed that superstrong electron-
withdrawing substituents can be obtained by replace-
ment of oxygen in various groups by an =NSO2CF3
moiety [33]. With p-fluorobenzaldehyde as an example
we showed that replacement of the carbonyl oxygen
atom in the aldehyde group (CH=O is a medium-
strength electron-withdrawing group, σp = 0.59) by
=NSO2CF3 gives CH=NSO2CF3 (σp = 1.00) which is
a considerably stronger electron acceptor than nitro
group (σp = 0.78), and its strength approaches that of
SO2CF3 group (σp = 1.04). Replacement of the oxygen
atom in carboxylic acid azides, amides, and oximes by
=NSO2CF3 group made it possible to perform previ-
ously unknown rearrangements, such as aza-Curtius,
aza-Hofmann, and aza-Lossen reactions [34]. We
believed that replacement of oxygen atom in quinones
by considerably more acceptor =NSO2CF3 group, as in
other cases, should give rise to unusual properties of
N-trifluoromethylsulfonyl 1,4-benzoquinone mono-
imines.
The goal of the present work was to synthesize new
N-alkyl(trifluoromethyl)sulfonyl 1,4-benzoquinone
monoimines, study their reactions with potassium thio-
cyanate, and compare the reactivities of N-arylsul-
fonyl, N-alkylsulfonyl, and N-trifluoromethylsulfonyl
1,4-benzoquinone monoimines toward that nucleo-
phile. The most widely used method for the prepara-
Adams and Looker [4] previously described the
only representative of N-alkylsulfonyl 1,4-benzo-
†
Deceased.
510

SYNTHESIS AND THIOCYANATION OF N-ALKYL(TRIFLUOROMETHYL)SULFONYL
511
Scheme 1.
OH
OH
O
R1
R2
R4
R3
R1
R2
R4
R3
R1
R2
R4
R3
NaHCO3
–HCl
[O]
AlkSO2Cl
+
NH2
NHSO2Alk
IIIa–IIIh
NSO2Alk
IVa–IVh
Ia, Ib
IIa–IIg
I, Alk = Me (a), Et (b); II, III, IV, Alk = Me (a–g), Et (h); R1 = R2 = R3 = R4 = H (a, h); R2 = R3 = R4 = H, R1 = Me (b); R1 = R3 =
R4 = H, R2 = Me (c); R3 = R4 = H, R1 = R2 = Me (d); R2 = R4 = H, R1 = R3 = Me (e); R2 = R3 = H, R1 = R4 = Me (f); R1 = R4 = H,
R2 = R3 = Me (g).
tion of N-substituted 1,4-benzoquinone imines is based
on reaction of p-aminophenols with acid chlorides,
followed by oxidation of N-acyl-substituted p-amino-
phenol [1–11]. According to this procedure we syn-
thesized new 4-(alkylsulfonylamino)phenols IIIa–
IIIh, and their oxidation gave N-alkylsulfonyl 1,4-ben-
zoquinone monoimines IVa–IVh (Scheme 1). The
yields were 30–60% (IVa–IVe, IVg, IVh) or 85%
(IVf) when lead tetraacetate or sodium dichromate in
acetic acid was used as oxidant. Compounds IVa–
IVh were obtained in quantitative yield by oxidation of
the corresponding N-substituted aminophenols IIIa–
IIIh with 4-(diacetoxy-λ3-iodanyl)toluene and freshly
prepared silver oxide in inert solvents (chloroform,
methylene chloride).
at δ 2.35 ppm; these findings indicate fast (on the
NMR time scale) Z,E-isomerization about the C=N
bond [35]. 2,6-Dimethyl derivative IVf showed in
1
the H NMR spectrum at room temperature separate
signals from the methyl groups as doublets at δ 2.09
and 2.10 ppm, while the 3-H and 5-H signals were
quartets at δ 6.75 and 7.71 ppm.
We were the first to develop procedures for the syn-
thesis of structural analogs of compounds IV, which
contained a trifluoromethylsulfonyl group on the nitro-
gen atom. By reaction of p-aminophenols IIa–IIg with
trifluoromethanesulfonic anhydride (V) we obtained
4-(trifluoromethylsulfonylamino)phenols VIa–VIg
(Scheme 2). As with compounds IVa–IVh, quantita-
tive yields of the corresponding quinone imines VIIa–
VIIg were attained using 4-(diacetoxy-λ3-iodanyl)-
toluene and silver oxide in inert solvents (chloroform,
methylene chloride).
The IR spectra of aminophenols IIIa–IIIh con-
tained absorption bands in the regions 3330–3520,
3215–3285, and 1300–1320, 1130–1145 cm–1, which
are typical, respectively, of stretching vibrations of
NH, OH, and SO2 groups. Quinone imines IVa–IVh
displayed in the IR spectra absorption bands at 1635–
1660 (C=O), 1545–1565 (C=N), and 1315–1325,
1140–1145 cm–1 (SO2). In the 1H NMR spectra of IVa–
IVg protons in the quinoid ring resonated at δ 6.50–
7.98, and signal from protons in the methylsulfonyl
group was located at δ 3.24–3.33 ppm. Protons in
positions 2 and 6 of the quinoid ring in compound IVg
Quinone imine VIIa having no substituents in the
quinoid ring was obtained by oxidation of N-substitut-
ed aminophenol VIa with silver oxide in chloroform or
methylene chloride, and the formation of VIIa was
19
confirmed by the IR and F NMR spectra, as well as
1
by the H NMR data when the oxidation was carried
out in CDCl3. However, our attempts to isolate com-
pound VIIa by distillation of the solvent under reduced
pressure resulted in the formation of an intractable
mixture of decomposition products. For subsequent
experiments quinone imine VIIa was generated in situ
1
appeared in the H NMR spectrum as a singlet at
δ 6.50, and protons in the methyl groups gave a singlet
Scheme 2.
OH
O
R1
R2
R4
R1
R2
R4
R3
[O]
IIa–IIg
+
(CF3SO2)2O
–CF3SO3H
R3
NHSO2CF3
NSO2CF3
VIIa–VIIg
V
VIa–VIg
VI, VII, R1 = R2 = R3 = R4 = H (a); R2 = R3 = R4 = H, R1 = Me (b); R1 = R3 = R4 = H, R2 = Me (c); R3 = R4 = H, R1 = R2 = Me (d);
R2 = R4 = H, R1 = R3 = Me (e); R2 = R3 = H, R1 = R4 = Me (f); R1 = R4 = H, R2 = R3 = Me (g).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

AVDEENKO et al.
512
in chloroform. Compound VIIc was isolated as an
orange–red undistillable oily substance, and we failed
to crystallize it.
ior of the newly synthesized compounds with the be-
havior of previously studied N-arylsulfonyl 1,4-benzo-
quinone monoimines. Thiocyanate ion SCN– is a soft
ambident nucleophile capable of reacting by either sul-
fur or nitrogen atom [37]. Depending on the substit-
uent on the nitrogen atom, benzoquinone imines can
react with thiocyanate ion in both directions [18, 20].
The structure of compounds VIa–VIg and VIIa–
VIIg was confirmed by elemental analyses and IR and
13
19
1H, C, and F NMR spectra. The IR spectra of VIa–
VIg contained absorption bands in the regions 3390–
3595, 3255–3295, and 1345–1365, 1135–1145 cm–1 due
to stretching vibrations of the NH, OH, and SO2
groups, respectively. Quinone imines VIIa–VIIg were
characterized by IR absorption bands at 1660–1695
(C=O), 1555–1570 (C=N), and 1365–1380, 1120–
1125 cm–1 (SO2).
As reported in [18], thiocyanation of N-(4-methyl-
phenyl) 1,4-benzoquinone monoimine gives 5-(4-meth-
ylphenylamino)-1,3-benzoxazole-2-thione. The reac-
tion involves initial addition of thiocyanate ion by the
nitrogen atom at the ortho position with respect to the
carbonyl group (1,4-addition pattern), followed by
intramolecular cyclization (Scheme 3).
Unlike analogous N-methylsulfonyl 1,4-benzoqui-
none monoimine (IVf), methyl protons in VIIf reso-
nated in the 1H NMR spectrum at room temperature as
one singlet at δ 2.14 ppm, and the 3-H and 5-H protons
in the quinoid ring gave a broadened singlet at
δ 7.26 ppm. These data suggest reduced barrier to Z,E-
isomerization in VIIf as compared to N-methylsul-
fonyl analog IVf [35]. Compounds VIa–VIg charac-
Scheme 3.
Me
O
N
Me
O
KSCN
AcOH
S
19
N
H
teristically displayed in the F NMR spectra a singlet
N
H
from fluorine atoms in the trifluoromethylsulfonyl-
amino group in the region δF –75.06 to –76.41, and the
corresponding signal of quinone monoimines VIIa–
VIIg was observed at δF –78.59 to –79.33 ppm.
We previously showed [20] that reactions of
N-aroyl, N-arylsulfonyl, and N-(N-arylsulfonylbenz-
imidoyl) 1,4-benzoquinone monoimines, i.e., com-
pounds characterized by a higher redox potential than
N-aryl 1,4-benzoquinone monoimines [36, 38], with
thiocyanate ion lead to N-substituted 5-amino-1,3-ben-
zoxathiol-2-ones. The product structure suggests addi-
tion of thiocyanate ion by the sulfur atom with forma-
tion of intermediate thiocyanate A. We presume
cyclization of the latter to 1,3-benzoxathiol-2-imine B
which then undergoes hydrolysis to N-substituted
5-amino-1,3-benzoxathiol-2-ones (Scheme 4). Inter-
mediates A and B were not isolated.
New N-trifluoromethylsulfonyl 1,4-benzoquinone
monoimines VIIa–VIIg were tested for their resistance
to hydrolysis. For this purpose, a few drops of water
were added to a solution of quinone imine VIIa–VIIg
in chloroform, and the mixture was stirred for 24 h. In
19
the F NMR spectra of the reaction mixtures we ob-
served a singlet at δF –79.60 to –79.33 ppm, typical of
trifluoromethanesulfonamide [34], together with the
signal belonging to the CF3SO2N= group in the initial
quinone imine. Under the above conditions, compound
VIIa underwent complete hydrolysis to 1,4-benzo-
quinone and trifluoromethanesulfonamide, quinone
imines VIIc and VIIg were hydrolyzed only partly (by
20–30%), and compounds VIIb, VIId–VIIf, and VIIh
turned out to be stable.
Scheme 4.
O
O
S
H
SCN–, H+
N
RN
RNH
According to published data, introduction of elec-
tron-withdrawing substituents considerably increases
redox potential of quinone imines, which should affect
their reactivity [36]. In the present work we examined
reactions of N-alkylsulfonyl and N-trifluoromethylsul-
fonyl 1,4-benzoquinone monoimines with potassium
thiocyanate. This reaction is one of the most studied
transformations of N-substituted 1,4-quinone imines
[18–20], so that it was possible to compare the behav-
A
O
S
NH
RNH
RNH
B
O
H2O
O
–NH3
S
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

SYNTHESIS AND THIOCYANATION OF N-ALKYL(TRIFLUOROMETHYL)SULFONYL
513
Thiocyanation of 2,6-disubstituted 1,4-benzoqui-
none monoimines was accompanied by their reduction
to the corresponding aminophenols [20], indicating
that the reaction with thiocyanate ion is regioselective
(1,4-addition). We performed thiocyanation of N-alkyl-
sulfonyl and N-trifluoromethylsulfonyl 1,4-benzoqui-
none monoimines IVa–IVh and VIIa–VIIg with
potassium thiocyanate in a mixture of acetic acid with
chloroform at different temperatures. From compounds
IVa–IVe, IVg, IVh, VIIa–VIIe, and VIIg at room
temperature we obtained 5-methyl(trifluoromethyl)sul-
fonylamino-1,3-benzoxathiol-2-ones VIIIa–VIIIg and
IXa–IXf (Scheme 5) whose structure was proved by
IR and NMR spectroscopy and elemental analysis.
were not reported previously. The IR spectrum of X
contained absorption bands due to stretching vibrations
of N–H (3334) and C=N bonds (1646 cm–1), while ab-
sorption bands typical of the initial quinonimine (1665,
1560 cm–1) or carbonyl group in 1,3-benzoxathiol-2-
one (1705–1775 cm–1) were absent.
Scheme 6.
O
KSCN, –30°C
VIIa
NH
S
F3CSO2NH
X
O
S
H2O
O
–NH3
F3CSO2NH
Scheme 5.
IXa
R1
Unlike 2,6-dimethyl-substituted N-arylsulfonyl,
N-aroyl, and N-(N-arylsulfonylbenzimidoyl) 1,4-ben-
zoquinone monoimines [20], thiocyanation of com-
pounds IVf and VIIf was not accompanied by their
reduction to the corresponding aminophenols IIIf and
VIf; in these cases, complex mixtures of products were
formed, and we failed to separate them.
R2
O
S
KSCN, 25°C
IVa–IVe, IVg, IVh
VIIa–VIIe, VIIg
O
R4SO2NH
R3
VIIIa–VIIIg, IXa–IXf
VIII, R4 = Me (a–f), Et (g); IX, R4 = CF3; VIII, IX, R1 =
R2 = R3 = H (a, g); R2 = R3 = H, R1 = Me (b); R1 = R3 = H,
R2 = Me (c); R3 = H, R1 = R2 = Me (d); R2 = H, R1 = R3 =
Me (e); R1 = H, R2 = R3 = Me (f).
The reaction of quinone imine VIIa with a soft
sulfur-centered nucleophile having no other nucleo-
philic centers, tetramethylammonium trifluorometh-
anethiolate Me4N+ –SCF3 [39] also involved nucleo-
phile addition at the ortho position with respect to the
carbonyl group in VIIa with formation of 2-trifluoro-
methylsulfanyl-4-trifluoromethylsulfonylaminophenol
(XI) (Scheme 7). The 19F NMR spectrum of compound
XI contained signals at δF –75.74 (CF3SO2NH) and
–42.48 ppm (CF3SO2).
As shown previously [20], 5-arylsulfonylamino-
1,3-benzoxathiol-2-ones are characterized by the pres-
ence of signals in the C NMR spectra at δC 123–124
13
(C3a), 143–146 (C7a), and 167–169 ppm (C=O). Analo-
gous signals were present in the 13C NMR spectrum of
VIIIa: δC 123.50 (C3a), 144.37 (C7a), 169.02 ppm
(C=O); these signals are consistent with the assumed
structure. The structure of VIIIa is also confirmed by
analysis of its 13C NMR spectrum recorded without de-
coupling from protons. The IR spectra of compounds
VIIIa–VIIIg and IXa–IXf contained a strong absorp-
tion band in the region 1705–1775 cm–1, which is
typical of stretching vibrations of the carbonyl group in
1,3-benzoxathiol-2-ones, whereas bands assignable to
initial quinone imines [1635–1695 (C=O) and 1545–
1570 cm–1 (C=N)] were absent.
Scheme 7.
OH
Me4N+ F3CS–
VIIa
F3CSO2NH
SCF3
XI
Aryl trifluoromethyl sulfides are generally synthe-
sized by replacement of chlorine atoms in the SCCl3
group by fluorine using anhydrous hydrogen fluoride
or SbF3 [40], by radical ion perfluoroalkylation of
thiols [41], and exchange of activated halogen atoms
with the use of CuSCF3, AgSCF3 [42], and trifluoro-
methanesulfenyl chloride CF3SCl [43]. The reaction of
quinone monoimines with MeN+ –SCF3 may be pro-
posed as an acceptable method for the introduction of
an SCF3 group into aromatic ring and for the prepara-
By thiocyanation of N-trifluoromethylsulfonyl
1,4-benzoquinone monoimine (VIIa) at –30°C we
succeeded in isolating intermediate B, 5-trifluoro-
methylsulfonylamino-1,3-benzoxathiol-2-imine (X),
and subsequent hydrolysis of compound X in polar
solvent gave 5-trifluoromethylsulfonylamino-1,3-benz-
oxathiol-2-one (IXa) (Scheme 6). Compounds like X
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

AVDEENKO et al.
spectrum, δ, ppm: 2.22 s (3H, 2-Me), 2.89 s (3H,
514
tion of phenols possessing two different fluorine-con-
taining groups (from N-trifluoromethylsulfonyl
1,4-benzoquinone monoimines).
3
4
MeSO2), 6.57–6.60 d.d (1H, 5-H, J = 8.4, J =
1.7 Hz), 6.64 d (1H, 3-H), 7.03 d (1H, 6-H), 8.72 br.s
(1H, NH), 9.40 br.s (1H, OH). Found, %: N 6.95, 6.99.
C8H11NO3S. Calculated, %: N 6.96.
EXPERIMENTAL
N-(4-Hydroxy-2,3-dimethylphenyl)methanesul-
fonamide (IIId). Yield 65%, mp 216–217°C. 1H NMR
spectrum, δ, ppm: 2.05 s (3H, 3-Me), 2.17 s (3H,
The IR spectra were recorded on a Bruker Vertex-
70 spectrometer from samples prepared as KBr pellets
(IIIa–IIIh, VIa–VIg, VIIIa–VIIIg, IXa–IXf, X) and
solutions in CHCl3 (IVa–IVh, VIIa–VIIg. The
1H NMR spectra were measured on a Varian VXR-300
spectrometer (300 MHz) from solutions in DMSO-d6
(IIIa–IIIh, VIa–VIg, VIIIa–VIIIg, IXb–IXf, X, XI),
CDCl3 (IVa–IVh, VIIa–VIIg), and acetone-d6 (IXa)
using tetramethylsilane as reference. The 13C NMR
spectra were obtained using the same instrument
(75.4 MHz) from solutions in CDCl3 (IVa, IVe, IVf,
VIIe, VIIf) and DMSO-d6 (VIIIa, IXe, X). The
19F NMR spectra were recorded on a Varian Gemini-
200 spectrometer (188.14 MHz) using trichlorofluoro-
methane as reference. The purity of the isolated com-
pounds was checked by TLC on Silufol UV-254 plates
using alcohol–chloroform (1:10), benzene–hexane
(10:1), or hexane–ethyl acetate (1:2) as eluent; spots
were visualized under UV light.
3
2-Me), 2.86 s (3H, MeSO2), 6.65 d (1H, 5-H, J =
8.6 Hz), 6.90 d (1H, 6-H), 8.75 s (1H, NH), 9.34 s (1H,
OH). Found, %: N 6.50, 6.55. C9H13NO3S. Calculated,
%: N 6.51.
N-(4-Hydroxy-2,5-dimethylphenyl)methanesul-
fonamide (IIIe). Yield 70%, mp 171–172°C. 1H NMR
spectrum, δ, ppm: 2.06 s (3H, 5-Me), 2.18 s (3H,
2-Me), 2.89 s (3H, MeSO2), 6.63 s (1H, 3-H), 6.93 s
(1H, 6-H), 8.69 s (1H, NH), 9.32 s (1H, OH). Found,
%: N 6.52, 6.55. C9H13NO3S. Calculated, %: N 6.51.
N-(4-Hydroxy-3,5-dimethylphenyl)methanesul-
fonamide (IIIf). Yield 72%, mp 130–131°C; pub-
lished data [44]: mp 129–134°C. 1H NMR spectrum, δ,
ppm: 2.13 s (6H, Me), 2.85 s (3H, MeSO2), 6.79 s (2H,
2-H, 6-H), 8.17 br.s (1H, NH), 9.10 br.s (1H, OH).
N-(4-Hydroxy-2,6-dimethylphenyl)methanesul-
fonamide (IIIg). Yield 75%, mp 164–165°C. 1H NMR
spectrum, δ, ppm: 2.24 s (6H, Me), 2.98 s (3H,
MeSO2), 6.48 s (2H, 3-H, 5-H), 8.54 s (1H, NH),
9.32 s (1H, OH). Found, %: N 6.50, 6.54. C9H13NO3S.
Calculated, %: N 6.51.
4-(Alkylsulfonylamino)phenols IIIa–IIIh (gen-
eral procedure). Alkanesulfonyl chloride Ia or Ib,
15 mmol, was slowly added under stirring to a sus-
pension of 1.26 g (15 mmol) of sodium hydrogen car-
bonate and 15 mmol of aminophenol IIa–IIg in 10 ml
of water, maintaining the temperature below 70°C. The
mixture was kept for 30 min until the reaction was
complete and cooled, and the precipitate was filtered
off and washed with water. Aminophenol IIId was re-
crystallized from acetic acid, and aminophenols IIIa–
IIIc and IIIe–IIIh were recrystallized from water.
N-(4-Hydroxyphenyl)ethanesulfonamide (IIIh).
1
Yield 51%, mp 109–111°C. H NMR spectrum, δ,
ppm: 1.20 t (3H, CH2Me, J = 7.2 Hz), 2.92–2.97 m
(2H, CH2), 6.73 d (2H, 3-H, 5-H, J = 8 Hz), 7.05 d
(2H, 2-H, 6-H, J = 9 Hz), 9.27 br.s (1H, NH), 9.33 br.s
(1H, OH). Found, %: N 6.92, 6.97. C8H11NO3S. Cal-
culated, %: N 6.96.
N-(4-Hydroxyphenyl)methanesulfonamide
(IIIa). Yield 70%, mp 156–157°C; published data [4]:
mp 154.5–155.5°C. 1H NMR spectrum, δ, ppm: 2.85 s
(3H, MeSO2), 6.73 d (2H, 3-H, 5-H, J = 8.7 Hz),
7.05 d (2H, 2-H, 6-H, J = 8.7 Hz), 9.17 br.s (1H, NH),
9.35 br.s (1H, OH).
4-(Trifluoromethylsulfonylamino)phenols VIa–
VIg (general procedure). A 250-ml reactor equipped
with a stirrer, dropping funnel, and reflux condenser
was charged with 0.06 mol of aminophenol IIa–IIg in
60 ml of anhydrous diethyl ether, the mixture was
cooled to 0°C in a stream of argon, and a solution of
8.46 g (0.03 mol) of trifluoromethansulfonic anhydride
(V) in 25 ml of diethyl ether was added dropwise
under stirring. The mixture was allowed to warm up to
room temperature over a period of 2 h and was left
overnight to complete the process. The mixture was
then poured into 100 ml of 10% hydrochloric acid, the
organic layer was separated, washed with a saturated
solution of sodium chloride and water to pH 5–6, and
N-(4-Hydroxy-3-methylphenyl)methanesulfon-
amide (IIIb). Yield 55%, mp 97–98°C. 1H NMR spec-
trum, δ, ppm: 2.09 s (3H, 3-Me), 2.88 s (3H, MeSO2),
6.73 d (1H, 5-H, 3J = 8.4 Hz), 6.87–6.90 d.d (1H, 6-H,
4J = 1.7 Hz), 6.93 d (1H, 2-H), 9.12 s (1H, NH), 9.28 s
(1H, OH). Found, %: N 6.93, 6.98. C8H11NO3S. Cal-
culated, %: N 6.96.
N-(4-Hydroxy-2-methylphenyl)methanesulfon-
1
amide (IIIc). Yield 62%, mp 148–150°C. H NMR
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SYNTHESIS AND THIOCYANATION OF N-ALKYL(TRIFLUOROMETHYL)SULFONYL
515
dried over MgSO4, the solvent was distilled off, and
the residue was recrystallized from benzene–hexane.
6.51 s (2H, 3-H, 5-H), 9.53 br.s (1H, NH), 10.73 br.s
(1H, OH). 19F NMR spectrum: δF –76.41 ppm, s (CF3).
Found, %: N 5.18, 5.21. C9H10F3NO3S. Calculated, %:
N 5.20.
Trifluoro-N-(4-hydroxyphenyl)methanesulfon-
amide (VIa). Yield 93%, mp 105–107°C; published
1
data [45]: mp 105–107°C. H NMR spectrum, δ, ppm:
N-(4-Oxocyclohexa-2,5-dien-1-ylidene)alkane-
and -trifluoromethanesulfonamides IVa–IVh and
VIIa–VIIg (general procedures). a. Silver oxide,
0.26 g (1.1 mmol), was added under stirring in
a stream of argon to a suspension of 1 mmol of com-
pound IIIa–IIIh or VIa–VIg in 20 ml of anhydrous
chloroform or methylene chloride. The mixture was
stirred for 24 h, the precipitate of silver was filtered
off, the solvent was distilled off under reduced pres-
sure, and the yellow–orange residue was recrystallized
from benzene–hexane (IVa–IVh) or chloroform–
hexane (VIIa–VIIg).
6.78 d (2H, 3-H, 5-H, J = 9 Hz), 7.05 d (2H, 2-H, 6-H,
J = 9 Hz), 9.68 br.s (1H, NH), 11.40 br.s (1H, OH).
19F NMR spectrum: δF –75.44 ppm, s (CF3).
Trifluoro-N-(4-hydroxy-3-methylphenyl)meth-
anesulfonamide (VIb). Yield 81%, mp 98–100°C.
1H NMR spectrum, δ, ppm: 2.10 s (3H, 3-Me), 6.76 d
3
4
(1H, 5-H, J = 8.7 Hz), 6.87–6.89 d.d (1H, 6-H, J =
1.7 Hz), 6.93 d (1H, 2-H), 9.55 br.s (1H, NH), 11.29 br.s
(1H, OH). 19F NMR spectrum: δF –75.08 ppm, s (CF3).
Found, %: N 5.45, 5.50. C8H8F3NO3S. Calculated, %:
N 5.49.
b. 4-(Diacetoxy-λ3-iodanyl)toluene, 0.34 g
(1 mmol), was added under stirring in a stream of
argon to a suspension of 1 mmol of compound IIIa–
IIIh or VIa–VIg in 20 ml of anhydrous chloroform or
methylene chloride. The mixture was stirred for 24 h,
the solvent was distilled under reduced pressure at
a temperature not exceeding 40°C, and the yellow–
orange residue was washed with hexane and recrystal-
lized from benzene–hexane (IVa–IVh) or chloroform–
hexane (VIIa–VIIg). The yields of compounds IVa–
IVh and VIIa–VIIg were quantitative.
Trifluoro-N-(4-hydroxy-2-methylphenyl)meth-
anesulfonamide (VIc). Yield 68%, mp 100–102°C.
1H NMR spectrum, δ, ppm: 2.22 s (3H, 2-Me), 6.59–
6.61 d.d (1H, 5-H, 3J = 8.7, 4J = 2.4 Hz), 6.68 d (1H,
3-H), 7.00 d (1H, 6-H), 9.64 br.s (1H, NH), 11.03 br.s
(1H, OH). 19F NMR spectrum: δF –75.96 ppm, s (CF3).
Found, %: N 5.49, 5.50. C8H8F3NO3S. Calculated, %:
N 5.49.
Trifluoro-N-(4-hydroxy-2,3-dimethylphenyl)-
methanesulfonamide (VId). Yield 80%, mp 142–
143°C. 1H NMR spectrum, δ, ppm: 2.07 s (3H, 3-Me),
3
2.16 s (3H, 2-Me), 6.66 d (1H, 5-H, J = 8.6 Hz),
N-(4-Oxocyclohexa-2,5-dien-1-ylidene)methane-
sulfonamide (IVa). mp 132–134°C; published data
[4]: mp 134°C. 1H NMR spectrum, δ, ppm: 3.29 s (3H,
6.86 d (1H, 6-H), 9.53 br.s (1H, NH), 10.97 br.s (1H,
OH). 19F NMR spectrum: δF –75.86 ppm, s (CF3).
Found, %: N 5.18, 5.21. C9H10F3NO3S. Calculated, %:
N 5.20.
3
4
MeSO2), 6.64–6.68 d.d (1H, 5-H, J = 9, J = 2.1 Hz),
6.73–6.76 d.d (1H, 3-H, 3J = 9 Hz), 7.01–7.05 d.d (1H,
4
13
6-H, J = 2.7 Hz), 7.94–7.98 d.d (1H, 2-H). C NMR
spectrum, δC, ppm: 39.81 (MeSO2), 127.23 (C3),
131.96 (C5), 132.66 (C2), 136.83 (C6), 161.14 (C=N),
187.00 (C=O).
Trifluoro-N-(4-hydroxy-2,5-dimethylphenyl)-
methanesulfonamide (VIe). Yield 46%, mp 129–
130°C. 1H NMR spectrum, δ, ppm: 2.06 s (3H, 5-Me),
2.18 s (3H, 2-Me), 6.66 s (1H, 3-H), 6.88 s (1H, 6-H),
19
9.52 s (1H, NH), 10.95 br.s (1H, OH). F NMR spec-
N-(3-Methyl-4-oxocyclohexa-2,5-dien-1-ylidene)-
methanesulfonamide (IVb). mp 114–116°C. 1H NMR
spectrum, δ, ppm: Z isomer (60%): 2.11 s (3H, 3-Me),
trum: δF –76.08 ppm, s (CF3). Found, %: N 5.19, 5.23.
C9H10F3NO3S. Calculated, %: N 5.20.
3
3.27 s (3H, MeSO2), 6.72 d (1H, 5-H, J = 10.2 Hz),
Trifluoro-N-(4-hydroxy-3,5-dimethylphenyl)-
methanesulfonamide (VIf). Yield 68%, mp 122–
6.93–6.96 d.d (1H, 6-H, 4J = 2.1 Hz), 7.76 d (1H, 2-H);
E isomer (40%): 2.11 s (3H, 3-Me), 3.27 s (3H,
1
123°C. H NMR spectrum, δ, ppm: 2.14 s (6H, Me),
3
MeSO2), 6.64 d (1H, 5-H, J = 10.2 Hz), 6.84 d (1H,
6.81 s (2H, 2-H, 6-H), 8.49 br.s (1H, NH), 11.35 br.s
(1H, OH). 19F NMR spectrum: δF –75.06 ppm, s (CF3).
Found, %: N 5.17, 5.20. C9H10F3NO3S. Calculated, %:
N 5.20.
2-H, 4J = 2.1 Hz), 7.89–7.92 d.d (1H, 6-H). Found, %:
N 7.01, 7.06. C8H9NO3S. Calculated, %: N 7.03.
N-(2-Methyl-4-oxocyclohexa-2,5-dien-1-ylidene)-
methanesulfonamide (IVc). mp 125–126°C. 1H NMR
spectrum, δ, ppm: 2.16 s (3H, 2-Me), 3.31 s (3H,
MeSO2), 6.57–6.60 d.d (1H, 5-H, 3J = 11.4, 4J = 3 Hz),
Trifluoro-N-(4-hydroxy-2,6-dimethylphenyl)-
methanesulfonamide (VIg). Yield 69%, mp 102–
1
103°C. H NMR spectrum, δ, ppm: 2.21 s (6H, Me),
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AVDEENKO et al.
516
6.59 d (1H, 3-H), 7.93 d (1H, 6-H). Found, %: N 6.99,
7.05. C8H9NO3S. Calculated, %: N 7.03.
Found, %: N 5.51, 5.55. C8H6F3NO3S. Calculated, %:
N 5.53.
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)methanesulfonamide (IVd). mp 96–98°C.
1H NMR spectrum, δ, ppm: 2.08 s (3H, 3-Me), 2.13 s
(3H, 2-Me), 3.30 s (3H, MeSO2), 6.59 d (1H, 5-H, 3J =
9.9 Hz), 7.90 d (1H, 6-H). Found, %: N 6.52, 6.59.
C9H11NO3S. Calculated, %: N 6.57.
Trifluoro-N-(2-methyl-4-oxocyclohexa-2,5-dien-
1-ylidene)methanesulfonamide (VIIc). H NMR
spectrum, δ, ppm: 2.19 s (3H, Me), 6.67 d (1H, 3-H,
4J = 3 Hz), 6.68–6.72 d.d (1H, 6-H, 3J = 12 Hz), 7.68 d
(1H, 5-H). 19F NMR spectrum: δF –78.81 ppm, s (CF3).
1
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)trifluoromethanesulfonamide (VIId). mp 74–
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)methanesulfonamide (IVe). mp 120–122°C.
1H NMR spectrum, δ, ppm: 2.07 d (3H, 5-Me, J =
1.5 Hz), 2.13 d (3H, 2-Me, J = 1.5 Hz), 3.29 s (3H,
MeSO2), 6.56 q (1H, 3-H), 7.72 q (1H, 6-H). 13C NMR
spectrum, δC, ppm: 16.09 (5-Me), 17.31 (2-Me), 43.23
(MeSO2), 127.55 (C6), 133.45 (C3), 144.79 (C2),
147.95 (C5), 165.82 (C=N), 186.31 (C=O). Found, %:
N 6.52, 6.60. C9H11NO3S. Calculated, %: N 6.57.
1
76°C. H NMR spectrum, δ, ppm: 2.12 s (3H, 3-Me),
3
2.15 s (3H, 2-Me), 6.69 d (1H, 5-H, J = 9.3 Hz),
7.64 d (1H, 6-H). 19F NMR spectrum: δF –78.99 ppm, s
(CF3). Found, %: N 5.21, 5.25. C9H8F3NO3S. Calculat-
ed, %: N 5.24.
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)trifluoromethanesulfonamide (VIIe). mp 65–
1
66°C. H NMR spectrum, δ, ppm: 2.14 d (3H, 5-Me,
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)methanesulfonamide (IVf). mp 83–84°C.
J = 1.5 Hz), 2.16 d (3H, 2-Me, J = 1.5 Hz), 6.64 q
(1H, 3-H), 7.47 q (1H, 6-H). 19F NMR spectrum:
4
1H NMR spectrum, δ, ppm: 2.09 d (3H, 5-Me, J =
13
δF –78.70 ppm, s (CF3). C NMR spectrum, δC, ppm:
4
2.1 Hz), 2.10 d (3H, 3-Me, J = 2.1 Hz), 3.25 s (3H,
16.26 (5-Me), 17.04 (2-Me), 118.61 q (CF3, J =
318.8 Hz), 128.04 (C6), 134.52 (C3), 147.19 (C2),
147.39 (C5), 169.96 (C=N), 185.63 (C=O). Found, %:
N 5.21, 5.26. C9H8F3NO3S. Calculated, %: N 5.24.
MeSO2), 6.75 m (1H, 6-H), 7.71 m (1H, 2-H).
13C NMR spectrum, δC, ppm: 16.06 (3-Me), 16.71
(5-Me), 43.03 (MeSO2), 126.98 (C2), 136.01 (C6),
145.23 (C3, C5), 165.06 (C=N), 186.48 (C=O). Found,
%: N 6.54, 6.59. C9H11NO3S. Calculated, %: N 6.57.
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)trifluoromethanesulfonamide (VIIf). mp 93–
1
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)methanesulfonamide (IVg). mp 153–154°C.
1H NMR spectrum, δ, ppm: 2.35 s (6H, 2-Me, 6-Me),
3.33 s (3H, MeSO2), 6.50 s (2H, 3-H, 5-H). Found, %:
N 6.51, 6.57. C9H11NO3S. Calculated, %: N 6.57.
94°C. H NMR spectrum, δ, ppm: 2.14 s (6H, Me),
7.26 br.s (2H, 2-H, 6-H). 19F NMR spectrum:
13
δF –79.28 ppm, s (CF3). C NMR spectrum, δC, ppm:
16.51 (Me), 118.70 q (CF3, J = 319.5 Hz), 130.7 br.s
(C2, C6), 147.53 (C3, C5), 169.08 (C=N), 185.69
(C=O). Found, %: N 5.23, 5.27. C9H8F3NO3S. Cal-
culated, %: N 5.24.
N-(4-Oxocyclohexa-2,5-dien-1-ylidene)ethane-
1
sulfonamide (IVh). mp 90–91°C. H NMR spectrum,
δ, ppm: 1.52 t (3H, CH2Me, J = 7.5 Hz), 3.31–3.39 m
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)trifluoromethanesulfonamide (VIIg). mp 64–
3
4
(2H, CH2Me), 6.64–6.67 d.d (1H, 5-H, J = 9, J =
3
1
2.7 Hz), 6.71–6.75 d.d (1H, 3-H, J = 12 Hz), 7.02–
66°C. H NMR spectrum, δ, ppm: 2.33 s (6H, Me),
4
6.58 s (2H, 3-H, 5-H). 19F NMR spectrum:
δF –79.33 ppm, s (CF3). Found, %: N 5.21, 5.26.
C9H8F3NO3S. Calculated, %: N 5.24.
7.05 d.d (1H, 6-H, J = 2.7 Hz), 7.98–8.01 d.d (1H,
2-H). Found, %: N 6.99, 7.04. C8H9NO3S. Calculated,
%: N 7.03.
Trifluoro-N-(4-oxocyclohexa-2,5-dien-1-ylidene)-
methanesulfonamide (VIIa). H NMR spectrum, δ,
ppm: 6.77 br.s (1H, 5-H), 6.81 br.s (1H, 3-H), 7.35 br.s
(1H, 6-H), 7.64 br.s (1H, 2-H). 19F NMR spectrum:
δF –78.59 ppm, s (CF3).
1,3-Benzoxathiol-2-ones VIIIa–VIIIg and IXa–
IXf (general procedure). A solution of 0.19 g (2 mmol)
of potassium thiocyanate in 10 ml of acetic acid was
added to a solution of 1 mmol of compound IVa–IVh
or VIIa–VIIg in 10 ml of chloroform. The mixture
was stirred for 24 h at room temperature and evap-
orated under reduced pressure, the residue was poured
onto ice, and the precipitate was filtered off, washed
with water, and recrystallized from aqueous acetic
acid.
1
Trifluoro-N-(3-methyl-4-oxocyclohexa-2,5-dien-
1-ylidene)methanesulfonamide (VIIb). mp 85–86°C.
1H NMR spectrum, δ, ppm: 2.10 s (3H, Me), 6.77 d
3
(1H, 5-H, J = 10.2 Hz), 7.10 br.s (1H, 6-H), 7.46 br.s
(1H, 2-H). 19F NMR spectrum: δF –78.85 ppm, s (CF3).
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517
N-(2-Oxo-1,3-benzoxathiol-5-yl)methanesulfon-
amide (VIIIa). Yield 57%, mp 190–192°C. H NMR
Trifluoro-N-(2-oxo-1,3-benzoxathiol-5-yl)meth-
anesulfonamide (IXa). Yield 62%, mp 159–161°C.
1H NMR spectrum (acetone-d6), δ, ppm: 6.92–6.95 d
(1H, 6-H), 7.30–7.33 d (1H, 7-H), 7.38 s (1H, 4-H).
19F NMR spectrum: δF –75.31 ppm, s (CF3). Found, %:
N 4.57, 4.60; S 21.25, 21.30. C8H4F3NO4S2. Calculat-
ed, %: N 4.68; S 21.43.
1
spectrum, δ, ppm: 3.02 s (3H, MeSO2), 7.19–7.22 d.d
3
4
(1H, 6-H, J = 8.7, J = 2.4 Hz), 7.47 d (1H, 7-H),
7.63 d (1H, 4-H), 9.91 s (1H, NH). 13C NMR spec-
trum, δC, ppm: 39.29 (MeSO2), 112.43 (C7), 115.31
(C4), 120.24 (C6), 123.50 (C3a), 135.52 (C5), 144.37
(C7a), 169.02 (C2). Found, %: N 5.75, 5.78; S 26.14,
26.19. C8H7NO4S2. Calculated, %: N 5.71; S 26.15.
Trifluoro-N-(7-methyl-2-oxo-1,3-benzoxathiol-5-
yl)methanesulfonamide (IXb). Yield 59%, mp 134–
1
N-(7-Methyl-2-oxo-1,3-benzoxathiol-5-yl)meth-
anesulfonamide (VIIIb). Yield 70%, mp 95–97°C.
1H NMR spectrum, δ, ppm: 2.33 s (7-Me), 3.01 s (3H,
MeSO2), 7.05 s (1H, 6-H), 7.45 s (1H, 4-H), 9.84 s
(1H, NH). Found, %: N 5.36, 5.45; S 24.65, 24.78.
C9H9NO4S2. Calculated, %: N 5.40; S 24.73.
136°C. H NMR spectrum, δ, ppm: 2.36 s (7-Me),
7.12 s (1H, 6-H), 7.57 s (1H, 4-H). 19F NMR spectrum:
δF –75.05 ppm, s (CF3). Found, %: N 4.42, 4.50;
S 20.45, 20.52. C9H6F3NO4S2. Calculated, %: N 4.47;
S 20.47.
Trifluoro-N-(6-methyl-2-oxo-1,3-benzoxathiol-5-
yl)methanesulfonamide (IXc). Yield 64%, mp 120–
N-(6-Methyl-2-oxo-1,3-benzoxathiol-5-yl)meth-
anesulfonamide (VIIIc). Yield 57%, mp 187–189°C.
1H NMR spectrum, δ, ppm: 2.36 s (6-Me), 3.03 s (3H,
MeSO2), 7.43 s (1H, 7-H), 7.70 s (1H, 4-H), 9.26 s
(1H, NH). Found, %: N 5.39, 5.45; S 24.68, 24.77.
C9H9NO4S2. Calculated, %: N 5.40; S 24.73.
1
123°C. H NMR spectrum, δ, ppm: 2.37 s (6-Me),
7.46 s (1H, 7-H), 7.72 s (1H, 4-H). 19F NMR spectrum:
δF –76.31 ppm, s (CF3). Found, %: N 4.43, 4.46;
S 20.40, 20.44. C9H6F3NO4S2. Calculated, %: N 4.47;
S 20.47.
N-(6,7-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
methanesulfonamide (VIIId). Yield 68%, mp 179–
181°C. 1H NMR spectrum, δ, ppm: 2.27 s (3H, 7-Me),
2.28 s (3H, 6-Me), 2.99 s (3H, MeSO2), 7.55 s (1H,
4-H), 9.28 s (1H, NH). Found, %: N 5.01, 5.18;
S 23.42, 23.51. C10H11NO4S2. Calculated, %: N 5.12;
S 23.46.
N-(6,7-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
trifluoromethanesulfonamide (IXd). Yield 68%,
mp 149–152°C. H NMR spectrum, δ, ppm: 2.27 s
(3H, 7-Me), 2.30 s (3H, 6-Me), 7.61 s (1H, 4-H).
19F NMR spectrum: δF –76.00 ppm, s (CF3). Found, %:
N 4.24, 4.29; S 19.55, 19.58. C10H8F3NO4S2. Calculat-
ed, %: N 4.28; S 19.59.
1
N-(4,7-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
methanesulfonamide (VIIIe). Yield 81%, mp 182–
184°C. 1H NMR spectrum, δ, ppm: 2.28 s (3H, 7-Me),
2.31 s (3H, 4-Me), 3.00 s (3H, MeSO2), 7.19 s (1H,
6-H), 9.26 s (1H, NH). Found, %: N 5.03, 5.11;
S 23.41, 23.51. C10H11NO4S2. Calculated, %: N 5.12;
S 23.46.
N-(4,7-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
trifluoromethanesulfonamide (IXe). Yield 81%,
mp 145–147°C. H NMR spectrum, δ, ppm: 2.29 s
(3H, 7-Me), 2.34 s (3H, 4-Me), 7.17 s (1H, 6-H).
13C NMR spectrum, δC, ppm: 15.07 (7-Me), 16.46
(4-Me), 117.63 (CF3), 120.36 (C7), 123.48 (C3a),
127.45 (C5), 128.68 (C6), 129.48 (C4), 145.17 (C7a),
168.01 (C2). 19F NMR spectrum: δF –77.20 ppm, s
(CF3). Found, %: N 4.19, 4.28; S 19.48, 19.58.
C10H8F3NO4S2. Calculated, %: N 4.28; S 19.59.
1
N-(4,6-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
methanesulfonamide (VIIIf). Yield 26%, mp 191–
192°C. 1H NMR spectrum, δ, ppm: 2.35 s (3H, 6-Me),
2.40 s (3H, 4-Me), 3.08 s (3H, MeSO2), 7.30 s (1H,
7-H), 9.08 s (1H, NH). Found, %: N 5.09, 5.12;
S 23.40, 23.50. C10H11NO4S2. Calculated, %: N 5.12;
S 23.46.
N-(4,6-Dimethyl-2-oxo-1,3-benzoxathiol-5-yl)-
trifluoromethanesulfonamide (IXf). Yield 76%,
1
mp 164–166°C. H NMR spectrum, δ, ppm: 2.35 s
(3H, 6-Me), 2.38 s (3H, 4-Me), 7.47 s (1H, 7-H).
19F NMR spectrum: δF –76.51 ppm, s (CF3). Found, %:
N 4.21, 4.26; S 19.58, 19.61. C10H8F3NO4S2. Calculat-
ed, %: N 4.28; S 19.59.
N-(2-Oxo-1,3-benzoxathiol-5-yl)ethanesulfon-
1
amide (VIIIg). Yield 65%, mp 150–151°C. H NMR
spectrum, δ, ppm: 1.21 t (3H, CH2Me, J = 7.5 Hz),
3.08–3.15 m (2H, CH2Me), 7.19–7.22 d.d (1H, 6-H,
3J = 9, 4J = 2.4 Hz), 7.45 d (1H, 7-H), 7.64 d (1H, 4-H),
9.99 s (1H, NH). Found, %: N 5.39, 5.45; S 24.67,
24.71. C9H9NO4S2. Calculated, %: N 5.40; S 24.73.
Trifluoro-N-(2-imino-1,3-benzoxathiol-5-yl)-
methanesulfonamide (X). A solution of 0.19 g
(2 mmol) of potassium thiocyanate in 10 ml of a 1:1
mixture of acetic acid with chloroform was cooled to
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AVDEENKO et al.
518
6. Avdeenko, A.P., Russ. J. Org. Chem., 2000, vol. 36,
–30°C, and a solution of 0.24 g (1 mmol) of compound
VIIa in chloroform was added dropwise under stirring
in a stream of argon. The color intrinsic to quinone
imine VIIa immediately disappeared. The mixture was
stirred for 2 h at –30°C, allowed to warm up to 0°C,
poured onto ice, and extracted with diethyl ether. The
extract was washed with ice water and dried over
MgSO4, the solvent was distilled off, and the residue
was recrystallized from benzene–ethyl acetate. Yield
45%, mp 137–138°C (decomp.). 1H NMR spectrum, δ,
ppm: 7.10–7.13 d.d (1H, 6-H, J = 8.7, J = 1.8 Hz),
7.30 d (1H, 7-H), 7.37 s (C=NH), 7.53 d (1H, 4-H),
10.67 br.s (1H, NH). 13C NMR spectrum, δC, ppm:
111.26 (C7), 118.31 (C4), 118.38 (CF3), 123.30 (C3a),
125.59 (C5), 130.85 (C6), 149.65 (C7a), 163.14 (C2).
19F NMR spectrum: δF –75.53 ppm, s (CF3). Found, %:
N 9.34, 9.37; S 21.48, 21.50. C8H5F3N2O3S2. Calculat-
ed, %: N 9.39; S 21.50.
p. 522.
7. Avdeenko, A.P., Yusina, A.L., and Yagupol’skii, L.M.,
Russ. J. Org. Chem., 2001, vol. 37, p. 1124.
8. Gebauer-Fülnegg, E. and Riesz, E., Monatsh. Chem.,
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3
4
Trifluoro-N-[4-hydroxy-3-(trifluoromethylsul-
fanyl)phenyl]methanesulfonamide (XI). A solution
of 0.24 g (1 mmol) of compound VIIa in 10 ml of
chloroform was cooled to 0°C, 1 ml of glacial acetic
acid was added under argon, and 0.18 g (1.1 mmol) of
tetramethylammonium trifluoromethanethiolate was
added in one portion. The mixture was stirred for 24 h
at room temperature and evaporated under reduced
pressure, and the residue was poured onto ice. The
precipitate was filtered off and recrystallized from ben-
11. Avdeenko, A.P., Konovalova, S.A., Sergeeva, A.G.,
Zubatyuk, R.I., Palamarchuk, G.V., and Shishkin, O.V.,
Russ. J. Org. Chem., 2008, vol. 44, p. 1765.
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Chem., 1955, vol. 67, p. 217.
13. Golubeva, I.S., Kubasova, I.Yu., Yavorskaya, N.P.,
Glibin, E.N., and Popova, E.B., Khim.-Farm. Zh., 2000,
vol. 34, p. 3.
1
zene. Yield 0.23 g (67%), mp 123°C. H NMR spec-
trum, δ, ppm: 7.16 d (1H), 7.27 s (1H), 7.40 d (1H),
9.47 br.s (1H, NH), 11.61 br.s (1H, OH). 19F NMR
spectrum, δF, ppm: –75.74 s (CF3SO2), –42.48 s
(CF3S). Found, %: S 18.41, 18.49. C8H5F6NO3S2. Cal-
culated, %: S 18.79.
14. Kalinichenko, V.N., Avdeenko, A.P., Lebedina, T.P., and
Blokh, G.A., Izv. Vyssh. Uchebn. Zaved., Ser. Khim.
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