Reactions of N-aryl(methyl, trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines with sodium sulfi nates

Article abstract of DOI:10.1134/S107042801202011X

In reactions with sodium sulfi nates of N-substituted 1,4-benzoquinone monoimines with the quinoid ring having free positions 2 and/or 6 the fraction of products of 1,4-addition of the sulfi nate ion grows in the series ArSO ₂ → MeSO₂ → CF₃SO₂. In the case of 2,6-dimethyl derivatives the 1,6-addition is preferable, and the amount of products of 6,1-addition decreases. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S107042801202011X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 2, pp. 221−233. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, O.N. Mikhailichenko, S.V. Shelyazhenko, V.V. Pirozhenko, L.M. Yagupol’skii, 2012, published in
Zhurnal Organicheskoi Khimii, 2012, Vol. 48, No. 2, pp. 233−244.
Reactions of N-Aryl(methyl, trifluoromethyl)sulfonyl-
1,4-benzoquinone Monoimines with Sodium Sulfinates
A. P. Avdeenkoa, S. A. Konovalovaa, O. N. Mikhailichenkoa,
S. V. Shelyazhenkob, V. V. Pirozhenkob, and L. M. Yagupol’skiib
aDonbass State Engineering Academy, Kramatorsk, 84313 Ukraine
е-mail: chimist@dgma.donetsk.ua
bInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received July 27, 2011
Abstract—In reactions with sodium sulfinates of N-substituted 1,4-benzoquinone monoimines with the quinoid
ring having free positions 2 and/or 6 the fraction of products of 1,4-addition of the sulfinate ion grows in the series
ArSO2 → MeSO2 → CF3SO2. In the case of 2,6-dimethyl derivatives the 1,6-addition is preferable, and the amount
of products of 6,1-addition decreases.
DOI: 10.1134/S107042801202011X
The introduction of superstrong electron-acceptor monoimines the reaction course is mainly governed by
substituents by replacement of an oxygen atom with
the group =NSO2CF3 [1] made it possible to perform
rearrangments previously unknown in organic chemistry:
aza-reactions of Curtius, Hofmann, and Lossen [2]. By
replacing the carbonyl group of the p-benzoquinone
with the =NSO2CF3 group N-trifluoromethylsulfonyl-
1,4-benzoquinone monoimines were synthesized [3] that
are structural analogs of N-methyl(aryl)sulfonyl-1,4-
benzoquinone monoimines. The van der Waals radii of the
methyl and trifluoromethyl groups have close values (0.21
and 0.18 nm [4]), therefore the reactivity difference of
these compounds should be governed mainly by different
electronic effects of these substituents.
the steric factor: the volume of the substituents in the
positions 2 and 6 of the quinoid ring [8].
No published information exists on the effect of the
steric and donor-acceptor properties of the substituents
at the sulfo group on the reactivity of the N-substituted
1,4-benzoquinone monoimines with respect to sodium
sulfinates.
The aim of this research was to determine the features
of reactions of N-alkyl(trifluoromethyl)sulfonyl-1,4-
benzoquinone monoimines with sodium arylsulfinates
containing in the aromatic ring donor (p-MeO, p-Me)
and acceptor (p-Cl, p-F) substituents, and with sodium
trifluoromethylsulfinate CF3SO2Na.
The reactivity of N-arylsulfonyl-1,4-benzoquinone
monoimines towards sodium arylsulfinates is sufficiently
well investigated [5–9]. The alkyl substituents in the
quinoid ring notably affect the reaction course [5–9].
Quinone monoimines with the quinoid ring having free
positions 2 and/or 6 react with sodium arylsulfinates as a
rule regiospecifically providing products of 1,4-addition
[6–8]. In reactions of N-4-(methylphenyl)sulfonyl-1,4-
benzoquinone monoimine [6] and its 2,5-dimethyl-
[7] and 3,5-dimethyl derivatives [8] formed up to
N-Methyl(trifluoromethyl)sulfonyl-1,4-benzoquinone
monoimines Ia–Ii, IIa–IIi were synthesized by
procedures described in [3, 10]. The results of reactions
between benzoquinone monoimines Ia–If, IIa–IIf and
sodium sulfinates IIIa–IIIf are presented in Scheme 1.
Reactions of quinone imines Ia–If, IIa–IIf with so-
dium sulfinates were carried out in acetic acid at boiling
and at room temperature, and also in a mixture of acetic
acid and chloroform at cooling to –10°С, therewith the
15% of the products of 1,6- and 6,1-addition. In the ratio quinone imine–sodium sulfinate was 1 : 2. This
case of N-arylsulfonyl-2,6-dialkyl-1,4-benzoquinone choice of conditions is due to the higher reactivity towards
221

AVDEENKO et al.
222
Scheme 1.
R1
R2
1,4
XSO2HN
OH
Y
R2
R1
R3
SO2
IVa–IVo, Va–Vn
+
O
XSO2N
SO2Na
Y
Me
IIIa–IIIf
R3
Ia–If, IIa–IIf
MeSO2
Y–SO2
6,1
N
OH
Me
VIa,VIb
X = Mе (I, IV), CF3 (II, V); I, II, R1 = R2 = R3 = Н (а); R2 = R3 = Н, R1 = Mе (b); R1 = R3 = Н, R2 = Mе (c); R3 = Н, R1 =
R2 = Mе (d); R2 = Н, R1 = R3 = Mе (e); R1 = Н, R2 = R3 = Mе (f); III, Y = 4-MеОC6H4 (а), 4-MеC6H4 (b), Ph (c), 4-ClC6H4
(d), 4-FC6H4 (e), CF3 (f); IV, Y = 4-MеОC6H4 (а, g, o), 4-MеC6H4 (b, i, k, m), Ph (c), 4-ClC6H4 (d, j, l, n), 4-FC6H4 (e,
h, p), CF3 (f); R1 = R2 = R3 = Н (а–f); R2 = R3 = Н, R1 = Mе (g, h); R1 = R3 = Н, R2 = Mе (i, j); R3 = Н, R1 = R2 = Mе (k,
l); R2 = Н, R1 = R3 = Mе (m, n); R1 = Н, R2 = R3 = Mе (o, p); V, Y = 4-MеОC6H4 (а, k, m), 4-MеC6H4 (b, i, l, n), Ph (c),
4-ClC6H4 (d, g, h, j), 4-FC6H4 (e), CF3 (f); R1 = R2 = R3 = Н (а–f); R2 = R3 = Н, R1 = Mе (g); R1 = R3 = Н, R2 = Mе (h);
R3 = Н, R1 = R2 = Mе (i, j); R2 = Н, R1 = R3 = Mе(k, l); R1 = Н, R2 = R3 = Mе (m, n); VI, Y = 4-MеОC6H4 (а), 4-FC6H4 (b).
nucleophiles of N-trifluoromethylsulfonyl-1,4-benzoqui-
none monoimines IIa–IIf: they react at room temperature
and even at cooling [3], in contrast to formerly studied
N-arylsulfonyl-1,4-benzoquinone monoimines whose
reactions with arylsodium sulfinates proceed only in
boiling acetic acid [5–9].
exclusively along the scheme of 1,4-addition giving
compounds Vm, Vn.
The temperature does not significantly affect the di-
rection of the reactions of quinone imines Ia–If, IIa–IIf.
The reactions of N-mesyl derivatives Ia–If at cooling
proceeded slower than at boiling, the decolorization of
the solution occurred not immediately, but in the course of
12 h. The reactions of N-trifluoromethyl derivatives IIa–
IIf took several seconds both at room temperature and at
cooling. In all events the nucleophilicity of the sulfinate
did not considerably affect the direction of the reaction.
The reaction products of N-mesyl and N-(trifluoro-
methylsulfonyl) derivatives Ia–If, IIa–IIf with sodium
sulfinates IIIа–IIIf we succeeded to isolate in all events,
only at boiling reagents IIa–IIf formed unidentified oily
substances.
The structure of all possible reaction products was
established with the help of 1Н and 19F NMR spectra. The
spectra were recorded both from the uncrystallized and
recrystallized reaction products, and from the products
isolated from the filtrate.
The results of the reactions of N-trifluoromethylsul-
fonyl derivatives IIa–IIf with salts IIIa–IIIf proved to
be quite unexpected compared with results published in
[7–9], which showed that for N-aroyl-1,4-benzoquinone
monoimines having at the nitrogen atom more acceptor
substituent than the arylsulfonyl group and with free posi-
tions 2 and/or 6 of the quinoid ring the amount of products
of arylsodium sulfinate addition to nitrogen and oxygen
atoms increased. In our case irrespective the increased
acceptor character of the substituent the opposite trend
was observed: For all N-trifluoromethylsulfonyl-1,4-
benzoquinone monoimines lacking substituents in the
positions 2 and 6 of the quinoid ring only the products
of 1,4-addition were isolated.
The reactions of quinone monoimines Ia–Ie, IIa–IIe
with salts IIIa–IIIf proceeded regiospecifically along the
scheme of 1,4-addition affording methanesulfonamides
IVа–IVn, Vа–Vl. In contrast to the N-arylsulfonyl-1,4-
benzoquinone monoimines [6, 7] the presence of the
products of 6,1-addition was detected only in the case of
3,5-dimethyl-substituted compound If, and their amount
reached 15% (VIа) and 14% (VIb). Yet 3,5-dimethyl-
N-trifluoromethyl-sulfonyl-1,4-benzoquinone monoi-
mine (IIf) reacted with arylsodium sulfinates IIIa, IIIb
It was suggested in [9] that two mechanisms exist of
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REACTIONS OF N-ARYL(METHYL,TRIFLUOROMETHYL)SULFONYL-1,4-BENZOQUINONE...
223
resulting in higher yields of the product of 1,4-addition
and in the higher reactivity of the quinone monoimines:
N-Trifluoromethyl derivatives react with sodium sul-
finates even in the cold and furnish only the products of
1,4-addition.
the addition of the sulfinate anion: 1) a nucleophilic ad-
dition of the sulfinate anion under the conditions of the
charge or orbital control (schemes of 1,4- and 6,3-addi-
tion); and 2) the addition of an arylsulfinate radical aris-
ing due to the oxidation of the arylsulfinate anion with
quinone imine (schemes of 1,6- and 6,1-addition). The
latter direction prevails at introducing more acceptor sub-
stituent to the nitrogen atom of the quinone monoimine,
i.e., in the case of N-aroyl-1,4-benzoquinone monoimines.
The results of the interaction of 2,6-dialkyl-N-methyl-
(trifluoromethyl)sulfonyl-1,4-benzoquinone monoimines
Ig–Ii, IIg–IIi with sodium sulfinates are presented in
Scheme 2.
For clear understanding of our results we performed
ab initio quantum-chemical calculations of unsubstituted
and 3,5(2,6)-dimethyl-substituted N-phenyl(methyl, tri-
fluoromethyl)sulfonyl-1,4-benzoquinone monoimines,
and also of N-benzoyl-1,4-benzoquinone monoimines
which like N-trifluoromethylsulfonyl derivatives had
a stronger acceptor substituent at the nitrogen atom than
N-arylsulfonyl derivatives, but showed different from N-
trifluoromethylsulfonyl derivatives reactivity with respect
to sulfinates. The optimization of the ground states with
respect to all geometrical parameters was carried out by
the standard procedure.
In the reactions of 2,6-dimethyl-N-mesyl-1,4-benzo-
quinone monoimine (Ig) with salts IIIа, IIId products
of 1,6-, 6,1-, and 6,3-addition were obtained. Their con-
tent was 72 (IXа), 23 (VIIа), 5 (XIа), and 66 (IXb), 29
(VIIb), 5% (XIb). In comparison with the corresponding
N-arylsulfonyl derivatives [8, 9] the content of the product
of 1,6-addition increased, of 6,3-addition decreased, and
the content in the mixture of the product of the 6,1-ad-
dition remained the same. The reaction in the cold gave
the products in the same ratio, but its duration increased
to several days.
For N-trifluoromethylsulfonyl analog IIg the main
products also resulted from the 1,6-addition: 65 (Xа),
56% (Xb). The content of the products of 6,1- and
6,3-addition was 5 (VIIIа), 5 (VIIIb), and 30 (XIIа),
39% (XIIb). Note that compared to N-methyl(aryl)-
sulfonyl-1,4-benzoquinone monoimines a significant
decrease in the amount of the product of the 6,1-addition
was observed probably due to the growth in the acceptor
characteristic of the substituent at the nitrogen atom [8, 9].
The influence of the substituent at the nitrogen atom
on the quinoid ring of the quinone monoimine may be
estimated by the energy of the donor-acceptor interac-
tions along the system of double bonds N=C–C=C–C=O,
namely, π(С1=О) → π*(С2=С3) + π(С2=С3) → π*(С4=N)
= Е1 and also π(С1=О) → π*(С5=С6) + π(С5=С6) →
π*(С4=N) = Е2, which are sufficiently strong in these
compounds. The analysis of calculation results showed
that in the series of substituents PhCO → PhSO2 →
MeSO2 → CF3SO2 the energies of the interactions Е1,
Е2, Е3 [π(С2=С3) → π*(С4=N)] and Е4 [π(С5=С6) →
π*(С4=N)] grew (Table 1) leading to the decrease in the
electron density and consequently to the negative charge
on the С2 and С6 atoms of the quinoid ring (Table 2).
In this series the LUMO energy of quinone imine also
decreased (Table 1) resulting in diminishing the energy
gap between the LUMO of the quinone monoimine and
the HOMO of the phenylsulfinate (–684.02 kJ mol−1)
and in increasing the possibility of the reaction to occur
along the scheme of the nucleophilic addition under the
orbital control. In the molecules of quinone monoimines
under consideration the distribution of the electron den-
sity on the LUMO has the maximum value on the atom
С2 of the quinoid ring and also increases in the series of
N-substituents PhSO2 → MeSO2 → CF3SO2 (Table 3).
We believe that these factors favor the growth of the activ-
ity of the atoms C2,6 with respect to the sulfinate anions
Thus in all cases of the reaction of 2,6-dimethyl-
N-methyl(trifluoromethyl)sulfonyl-1,4-benzoquinone
monoimines (Ig, IIg) with salts IIIа–IIIe the product
of 1,6-addition prevailed. According to calculations
2,6-dimethyl-substituted quinone monoimines possess
the largest value of the LUMO energy as compared with
analogous 3,5-dimethyl-substituted and unsubstituted in
the quinoid ring quinone monoimines (Table 1) that leads
to the increase in the energy gap between the quinone
imine and the sulfinate and to lower probability of the
nucleophilic addition of sulfinate to the quinoid ring of
quinone monoimine at the orbital control. In the series of
the substituents PhSO2 → MeSO2 → CF3SO2 the local-
ization of LUMO on the free atoms С3,5 of the quinoid
ring in 2,6-dimethylquinone monoimines also decreases
(Table 3). As a result for the 2,6-dimethyl-substituted
quinone monoimines the process of one-electron transfer
leading to the conversion of the arylsulfinate anion into
arylsulfinate radical becomes more feasible, and the qui-
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AVDEENKO et al.
224
Table 1. Energies of donor-acceptor interactions and LUMO in the molecules of N-phenyl(methyl, trifluoromethyl)sulfonyl- and
N-benzoyl-1,4-benzoquinone monoimines
R1
R2
3
2
X
4
1
N
O
5
6
R1
R2
Energy, kJ mol−1
Type of interaction
R1, R2
X = PhCO
102.91
X = PhSO2
X = MeSO2
113.95
X = CF3SO2
118.88
π(С1=О) →π*(С2=С3)
+ π(С2=С3) →π*(С4=N)
(Е1)
R1 = R2 = H
112.40
R1 = Me, R2 = H
107.59
118.59
120.13
125.57
R1 = H, R2 = Me
R1 = R2 = H
100.19
96.56
111.69
101.32
111.82
103.08
118.46
108.18
π(С1=О) →π*(С5=С6) +
π(С5=С6) →π*(С4=N) (Е2)
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
100.65
93.72
75.49
105.80
97.64
84.52
107.68
98.06
85.94
113.40
105.00
90.20
π(С2=С3) → π*(С4=N) (Е3)
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
81.64
73.02
92.25
83.77
93.72
83.81
98.56
89.79
π(С5=С6) → π*(С4=N) (Е4)
69.39
73.74
75.32
80.05
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
74.82
79.80
81.38
86.82
67.21
70.47
70.68
77.29
Е (LUMO)
–364.97
–341.74
–340.45
–383.93
–360.43
–366.53
–393.96
–368.67
–375.00
–437.30
–410.10
–417.09
R1 = Me, R2 = H
R1 = H, R2 = Me
Table 2. Charges on carbon atoms of quinoid ring in N-phenyl(methyl, trifluoromethyl)sulfonyl- and N-benzoyl-1,4-benzoquinone
monoimines
R1
R2
3
5
2
6
X
4
1
N
O
R1
R2
Charge, au of charge
Atom
R1, R2
X = PhCO
X = PhSO2
X = MeSO2
X = CF3SO2
С2
R1 = R2 = H
R1 = H, R2 = Me
R1 = R2 = H
–0.244
–0.249
–0.255
–0.262
–0.232
–0.239
–0.252
–0.257
–0.229
–0.238
–0.249
–0.254
–0.216
–0.225
–0.239
–0.246
С6
R1 = H, R2 = Me
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REACTIONS OF N-ARYL(METHYL,TRIFLUOROMETHYL)SULFONYL-1,4-BENZOQUINONE...
225
Scheme 2.
R
XSO2
6,1-
N
OH
YSO2
R
VIIа_VIIb, VIIIа, VIIIb
R
R
1,6-
XSO2HN
O SO2Y
R
R
IXа_IXf, Xа, Xb
Y SO Na
IIIа_IIIe
XSO2N
O +
2
R
6,3-
[H]
XSO2HN
YSO2
OH
Ig_Ii, IIg_IIi
R
XIа, XIb, XIIа, XIIb
Bu-t
OH
XSO2HN
Bu-t
XIII, XIV
X = Mе (I, VII, IX, XI, XIII), CF3 (II, VIII, X, XII, XIV); I, II, R = Mе (g), i-Pr (h), t-Bu (i); III, Y = 4-MеОC6H4 (а),
4-MеC6H4 (b), Ph (c), 4-ClC6H4 (d), 4-FC6H4 (e); VII, IX, XI, R = Mе, Y = 4-MеОC6H4 (а), 4-ClC6H4 (b); R = i-Pr, Y =
4-MеОC6H4 (c), 4-ClC6H4 (d); R = t-Bu, Y = 4-MеОC6H4 (e), 4-ClC6H4 (f); VIII, X, XII, R = Mе, Y = 4-MеОC6H4 (a),
4-MеC6H4 (b).
Table 3. LUMO density on carbon atoms of quinoid ring in N-phenyl(methyl, trifluoromethyl)sulfonyl- and N-benzoyl-1,4-
benzoquinone monoimines
R1
R2
3
5
2
6
X
4
1
N
O
R1
R2
LUMO density
X = MeSO2
Atom of quinoid
ring
R1, R2
X = PhSO2
X = CF3SO2
С2
С6
С3
С5
R1 = R2 = H
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
R1 = Me, R2 = H
R1 = H, R2 = Me
R1 = R2 = H
R1 = Me, R2 = H
R1 = H, R2 = Me
0.084
0.128
0.086
0.070
0.098
0.068
0.068
0.076
0.076
0.064
0.065
0.069
0.085
0.128
0.086
0.071
0.100
0.068
0.066
0.073
0.070
0.062
0.064
0.065
0.089
0.124
0.092
0.071
0.094
0.010
0.061
0.065
0.070
0.055
0.055
0.059
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AVDEENKO et al.
226
none monoimine transforms into a quinone monoimine
radical. Further the quinone monoimine radical reacts
with the sulfinate radical along the schemes of 1,6- and
6,1-addition.
(–79.6 × –80.2 ppm), hydrolysis product of quinone
imine IIi [1].
On recrystallization from aqueous acetic acid of the
mixtures of reaction products obtained from imines Ig,
Ih and salt IIId we succeeded to isolate two individual
products of 1,6-addition, amides IXb, IXd.
The predominant formation of the products of sulfinate
1,6-addition to the 2,6-dimethyl-substituted quinone
imines may be ascribed to a supplementary stabiliza-
tion by the methyl groups of the radical center on the
oxygen atom owing to the hyperconjugation effect. The
decrease in the amount of products obtained by the addi-
tion to nitrogen atom of 2,6-dimethyl-1,4-benzoquinone
monoimines in the series of the nitrogen substituents
PhSO2 → MeSO2 → CF3SO2 is due to the increase in
the acceptor qualities of the substituent at this atom and
consequently to the diminishing negative charge of the
nitrogen atom of the quinone monoimine radical.
In the case of N-mesyl-1,4-benzoquinone monoimines
Ig–Ii owing to the more bulky substituents in the ortho-
position with respect to the carbonyl group the amount
of the products of 1,6-addition decreases, and that of
the products of 6,1-addition increases which may be at-
tributed to the effect of the steric factors and also to the
diminished or lacking conjugation effect in the event of
the isopropyl and tert-butyl groups in the positions 2 and
6. Besides the introduction into the ortho-position with
respect to the carbonyl group in 2,6-dialkyl-substituted
quinone imines Ig–Ii, IIg–IIi of substituents more bulky
than the methyl group impedes the reaction to proceed
along the scheme of 6,3-addition; the corresponding
products were found only for compounds Ig, IIg. The
reduction of N-trifluoromethylsulfonyl-2,6-di-tert-butyl-
1,4-benzoquinone monoimine IIi in the reaction with
sodium sulfinates IIIа, IIId apparently originates from
the infeasibility of the 1,6-addition because of the bulk
of the substituent in the quinoid ring and also due to the
lack of the hyperconjugation effect, and the 6,1-addition
becomes unfavorable due to the increased acceptor prop-
erties of the substituent at the nitrogen atom.
The reactions of 2,6-diisopropyl derivative Ih with
salts IIIа, IIId required more severe conditions (boiling
in glacial acetic acid over 7 h). In this case the content
of the products of the 1,6- and 6,1-addition reached 44
(IXc), 59 (IXd) and 56 (VIIc), 41% (VIId). The same
products ratios were previously observed for N-arylsul-
fonyl analogs [49–52 (1,6-) and 48–51% (6,1-)] [10, 11].
With N-trifluoromethylsulfonyl derivative IIh complex
mixtures of compounds were obtained whose composition
we failed to determine.
In the reaction of N-mesylimine Ii with salts IIIа, IIId
at boiling in the glacial acetic acid for 10 h up to 5% of
amide XIII formed, the reduction product of quinone im-
ine Ii. The mixture also contained the hydrolysis product
of the initial imine, 2,6-di-tert-butyl-1,4-benzoquinone.
The content of products of 6,1- and 1,6-addition (not ac-
counting for compound XIII and the hydrolysis product)
was 86 (VIIe), 85 (VIIf) and 14 (IXe), 15% (IXf). The
content in the mixture of the product of 6,1-addition was
somewhat higher than in the case of N-arylsulfonyl-1,4-
benzoquinone monoimines [55–65 (6,1-) and 35–45%
(1,6-)] [8, 9].
The structure and composition of obtained compounds
IV–XIV were proved by IR and 1Н, 19F NMR spectros-
copy and by elemental analysis.
The analysis of the mixtures of products of the reac-
tions between quinone imines If–Ii with sodium aryl-
sulfinates was performed based on the data of [6–8, 11].
According to [11], the singlet signal of the protons of the
MeSO2 group of N-phenylmethanesulfonamide appeared
in the 1Н NMR spectrum in the region δ 3.00 ppm, and in
the spectrum of N-mesyl-N-phenylmethanesulfonamide,
at δ 3.40 ppm, namely, the substitution of a hydrogen
atom attached to nitrogen resulted in the downfield shift
of the protons of MeSO2 group. In the spectra of products
of 1,4- and 1,6-addition IVа–IVp, IXа–IXf the proton
signals of the mesyl group are observed in the region δ
2.94–3.04 and 3.01–3.03 ppm respectively, whereas in
the products of 6,1-addition VIа, VIb, VIIа–VIIf they
are located more downfield, 3.54–3.66 ppm. According
to [8], the chemical shifts of the aromatic protons of the
aminophenol fragment in the N-arylsulfonyl derivatives
The reaction of N-trifluoromethylsulfonyl analog IIi
with salts IIIа, IIId was carried out in a mixture of glacial
acetic acid and chloroform at heating to 50°С for several
days for at the room temperature the reaction proceeded
very slow. According to the 1Н NMR data the main reac-
tion product was amide XIV, the product of reduction of
quinone imine IIi. The 1Н NMR spectrum contained also
signals of 2,6-di-tert-butyl-1,4-benzoquinone (singlets
in the region 1.24 and 6.51 ppm), and in the 19F NMR
spectrum, the signal of the trifluoromethanesulfonic acid
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227
had the characteristic values 6.56–6.69 (6,1-addition)
and 6.94–7.17 ppm (1,6-addition). In the spectra of the
corresponding reaction products obtained from N-mesyl-
1,4-benzoquinone monoimines and sodium arylsulfinates
(compounds VIа, VIb, VIIа–VIIf, IXа–IXf) the signals
of the aromatic protons appear in the region δ 6.48–6.79
and 6.92–7.24 ppm respectively.
tions of the N-trifluoromethylsulfonyl-1,4-benzoquinone
monoimines with sodium sulfinates proceed strictly re-
giospecifically along the scheme of 1,4-addition.
The direction of the sulfinates reaction along 1,6- and
6,1-addition occurs by the mechanism of one electron
transfer. In event of 2,6-dimethyl-N-aryl(methyl, tri-
fluoromethyl)sulfonyl-1,4-benzoquinone monoimines
the products of 1,6-addition prevail apparently due to the
supplementary stabilization of the radical center on the
oxygen atom by the hyperconjugation with the methyl
groups.
The fluorine signals in the 19F NMR spectra of the
products of 1,4-addition of sodium sulfinates to quinine
imines IIa−IIf were attributed based on the published
data on the chemical shifts of the =NSO2CF3 group in
various compounds [3, 12]. The singlet of the trifluoro-
methylsulfonyl group of compounds Va–Vn appeared in
the 19F NMR spectra in the region δ –74.8 to –76.4 ppm.
It is known that in the spectrum of N-(4-hydroxyphenyl)-
1,1,1-trifluoromethanesulfonamides it is observed in the
region δ –75.1 to –76.4 ppm [3], and in the spectrum of
N-phenyl-N-(trifluoromethylsulfonyl)-1,1,1-trifluoro-
methanesulfonamide, at –78.9 ppm [12]. In the spectra
of the products of the addition at the oxygen atom and
of products of the 6,3-addition the singlets of the tri-
fluoromethylsulfonyl group are observed in the region
δ –75.6 to –75.7 and –75.3 to –75.4 ppm respectively,
and of the products of the addition at the nitrogen atom
VIIIa, VIIIb, at –75.8 to –75.9 ppm. The signals of the
aromatic protons of the aminophenol fragment in the
N-trifluoromethylsulfonyl derivatives are observed at
δ 6.71–6.75 (6,1-addition) (VIIIa, VIIIb), 7.01–7.05
(1,6-addition) (Xa, Xb), and 7.04–7.09 ppm (6,3-addi-
tion) (XIIa, XIIb).
Consequently, the reactivity of N-trifluoromethylsul-
fonyl-1,4-benzoquinone monoimines on the one hand is
characteristic of N-sulfonyl derivatives and on the other
hand, the presence of a strong trifluoromethyl group
leads to the appearance of the properties characteristic
of N-aroyl-1,4-benzoquinone monoimines.
EXPERIMENTAL
All calculations were carried out using the program
GAUSSIAN 03 [13]. The molecular structure of com-
pounds under study was calculated in the framework
of the density functional theory using B3LYP func-
tional [14–19]. In the calculations the standard basic
set 6-31+G(d) was used [20, 21]. The conjugation and
hyperconjugation interactions in the molecules were
investigated in the framework of the theory of natural
binding orbitals (NBO) [22] applying the program NBO
5.0 [23].
In the IR spectra of compounds IXb, IXd absorp-
tion bands in the region 3310–3350 cm–1 are present
belonging to NH group. The characteristic absorption
bands of the products of the 1,4-addition IVa–IVp, Va–
Vn are observed in the interval 3160–3270 (NH) and
3270–3400 cm–1 (OH).
IR spectra of compounds synthesized were recorded
on a spectrophotometer Bruker Vertex-70 from pellets
with KBr (compounds IV–XIV) and in CHCl3 (com-
1
pounds I, II). Н NMR spectra were registered on a
spectrometer Varian VXR-300 (300 MHz) from solution
in DMSO-d6 of compounds IV, Vа–Ve, Vg–Vn, VI–XIV
and in CDCl3 of compounds I, II, Vf. The chemical shifts
are reported with respect to TMS. 13С NMR spectra were
obtained on a spectrometer Varian VXR-300 (75.4 MHz)
from solutions in CDCl3. 19F NMR spectra were taken
on an instrument Varian Gemini-200 (188.14 MHz),
the chemical shifts are reported with respect to fluo-
rotrichloromethane. The purity of quinone imines and
the products of their reactions was checked by TLC on
Silufol UV-254 plates, eluents ethanol–chloroform, 1 :
10, benzene–hexane, 10 : 1, hexane–ethyl acetate, 1 : 2,
development under UV irradiation.
Therefore as a result of the performed research it
was established that in the series of 1,4-benzoquinone
monoimines with the N-substituents PhSO2 → MeSO2 →
CF3SO2 having the free positions 2 and/or 6 of the quinoid
ring with growing acceptor property of the substituent
at the nitrogen atom the LUMO energy of the quinine
monoimine decreased and the influence of the substituent
on the С=С bonds of the quinoid ring grew accordingly
raising the activity of the positions 2 and 6 of the quinoid
ring with respect to the sulfinate ion and leading to the
prevalence of the 1,4-addition to the ring of the quinone
monoimine at the orbital control. As a result the reac-
Quinone imines Iа–Ii, IIа–IIi were prepared by
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AVDEENKO et al.
228
procedure [3] by the oxidation of the corresponding
aminophenols with silver oxide or with 4-(diacetoxyiodo)
toluene in chloroform or dichloromethane. The charac-
teristics of compounds Iа–Ig, IIа–IIg are in agreement
with those published in [3], of compound Ih, in [10].
compound from glacial acetic acid it was precipitated by
adding a double volume of water. The precipitate was
filtered off and dried.
b. To a solution of 2 mmol of quinone imine Iа–Ii,
IIа–IIi in 10 ml of chloroform or dichloromethane was
added dropwise a solution of 4 mmol of salt IIIа–IIIf
in 10 ml of glacial acetic acid at room temperature or at
cooling to –10°С while passing argon flow. Reactions
of quinone imines IIа–IIi were monitored by 19F NMR
spectra. Quinone imines Ig–Ii, IIg–IIi reacted within
10–12 h at 50°С, quinone imines Iа–If, within 12 h
without heating. On the completion of the reaction the
solution was evaporated in a vacuum, the residue was
poured on ice at stirring, the colorless precipitate was
worked up as in procedure а.
Sodium sulfinates IIIа–IIIe were obtained by pro-
cedure [24], reagent IIIf, by method [25].
2,6-Diisopropyl-N-mesyl-1,4-benzoquinone monoi-
mine (Ih). Yield 92%, mp 67–68°С (mp 67–68°C [10]).
1Н NMR spectrum, δ, ppm: 1.13 d (6Н, 6-СНMе2,
J 6.9 Hz), 1.16 d (6Н, 2-СНMе2, J 7.2 Hz), 3.00–3.15 m
(2Н, 2,6-СНMе2), 3.25 s (3Н, MеSO2), 6.67 d (1Н, Н5,
J5,3 2.4 Hz), 7.63 d (1Н, Н3). Found, %: N 5.11, 5.13.
C13H19NO3S. Calculated, %: N 5.20.
2,6-Di-tert-butyl-N-mesyl-1,4-benzoquinone
1
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)
phenyl]methanesulfonamide (IVа). Yield 87%, mp
monoimine (Ii). Yield 91%, mp 88–90°С. Н NMR
spectrum, δ, ppm: 1.29 br.s (18Н, t-Bu), 3.24 br.s (3Н,
MеSO2), 6.70 br.s (1Н, Н5), 7.69 br.s (1Н, Н3). 13С NMR
spectrum, δ, ppm: 29.40 (2,6-СMе3), 35.89 (2-СMе3),
36.37 (6-СMе3), 43.11 (MеSO2), 124.05 (С3), 132.92
(С5), 157.24 (С2), 157.53 (С6), 166.23 (C=N), 186.15
(C=O). Found, %: N 4.75, 4.77. C15H23NO3S. Calculated,
%: N 4.71.
1
80–82°С. Н NMR spectrum, δ, ppm: 2.94 s (3Н,
MеSO2), 3.83 s (3Н, MеО), 6.87 d (1Н, Н5, J5,6 9.0 Hz),
7.11 d (2Н, Н3',5', 4-MеOС6Н4, J 8.7 Hz), 7.32 d.d (1Н,
Н6, J6,5 9.0 Hz, J6,2 2.4 Hz), 7.79 d (1Н, Н2, J2,6 2.4 Hz),
7.84 d (2Н, Н2'6', 4-MеOС6Н4, J 8.7 Hz), 9.58 br.s (1Н,
NН), 10.73 s (1Н, ОН). Found, %: N 3.89, 3.93. C14H-
15NO6S2. Calculated, %: N 3.92.
2,6-Diisopropyl-N-trifluoromethylsulfonyl-1,4-
benzoquinone monoimine (IIh). Yield 91%, mp
N-(4-Hydroxy-3-tosylphenyl)methanesulfonamide
(IVb). Yield 88%, mp 153–154°С. 1Н NMR spectrum,
δ, ppm: 2.38 s (3Н, Ts), 2.95 s (3Н, MеSO2), 6.88 d (1Н,
Н5, J5,6 9.0 Hz), 7.35 d.d (1Н, Н6, J6,5 9.0, J6,2 2.4 Hz),
7.39 d (2Н, Н3',5', Ts, J 8.1 Hz), 7.78 d (2Н, Н2',6', Ts,
J 8.1 Hz), 7.80 d (1Н, Н2, J2,6 2.4 Hz), 9.61 s (1Н, NН),
10.73 s (1Н, ОН). Found, %: N 3.99, 4.03. C14H15NO5S2.
Calculated, %: N 4.10.
1
51– 52°С. Н NMR spectrum, δ, ppm: 1.05 d (12Н,
2,6-СНMе2, J 6.6 Hz), 2.97–3.10 m (2Н, 2,6-СНMе2),
6.85 br.s (2Н, Н3,5). 19F NMR spectrum, δ, ppm: –79.03 s
(CF3). 13С NMR spectrum, δ, ppm: 20.44 (2,6-СНMе2),
26.80 (2,6-СНMе2), 118.70 q (CF3, J 319.5 Hz), 128.47
(С3,5), 156.06 (С2,6), 169.11 (C=N), 183.44 (C=O).
Found, %: N 4.35, 4.38. C13H16F3NO3S. Calculated, %:
N 4.33.
N-[4-Hydroxy-3-(phenylsulfonyl)phenyl]methane-
sulfonamide (IVc). Yield 78%, mp 150–151°С. 1Н NMR
spectrum, δ, ppm: 2.96 s (3Н, MеSO2), 6.91 d (1Н,
Н5, J5,6 9.0 Hz), 7.37 d.d (1Н, Н6, J6,5 9.0, J6,2 2.4 Hz),
7.58–7.92 m (5Н, Ph), 7.83 d (1Н, Н2, J2,6 2.4 Hz), 9.62 s
(1Н, NН), 10.78 s (1Н, ОН). Found, %: N 4.18, 4.23.
C13H13NO5S2. Calculated, %: N 4.28.
2,6-Di-tert-butyl-N-trifluoromethylsulfonyl-
1,4-benzoquinone monoimine (IIi). Yield 90%, mp
1
68–70°С. Н NMR spectrum, δ, ppm: 1.24 br.s (18Н,
t-Bu), 6.99 br.s (2Н, Н3,5). 19F NMR spectrum, δ, ppm:
–79.07 с (CF3). Found, %: N 4.03, 4.06. C15H20F3NO3S.
Calculated, %: N 3.99.
N-[4-Hydroxy-3-(4-chlorophenylsulfonyl)phenyl]-
methanesulfonamide (IVd). Yield 76%, mp 179–180°С.
1Н NMR spectrum, δ, ppm: 2.97 s (3Н, MеSO2),
6.93 d (1Н, Н5, J5,6 9.0 Hz), 7.38 d.d (1Н, Н6, J6,5 9.0,
J6,2 2.7 Hz), 7.69 d (2Н, Н3',5', 4-ClС6Н4, J 8.4 Hz),
7.82 d (1Н, Н2, J2,6 2.7 Hz), 7.92 d (2Н, Н2',6', 4-ClС6Н4,
J 8.4 Hz), 9.64 s (1Н, NН), 10.87 s (1Н, ОН). Found, %:
N 3.89, 3.91. C13H12ClNO5S2. Calculated, %: N 3.87.
Reaction of quinone imines Iа–Ii, IIа–IIi with
sodium sulfinates IIIа–IIIf. а. To a stirred solution of
2 mmol of quinone imine Iа–Ii in 20 ml of glacial acetic
acid at room temperature or at boiling was added in one
portion 4 mmol of dry salt IIIа–IIIf. After the solution
decolorized it was cooled and poured on ice. The colorless
precipitate was filtered off and washed in succession with
cold and warm water.At the recrystallization of the target
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229
N-[4-Hydroxy-3-(4-fluorophenylsulfonyl)phenyl]
methanesulfonamide (IVe). Yield 81%, mp 179–180°С.
1Н NMR spectrum, δ, ppm: 2.96 s (3Н, MеSO2),
6.92 d (1Н, Н5, J5,6 8.7 Hz), 7.36 d.d (1Н, Н6, J6,5 8.7,
J6,2 2.4 Hz), 7.41–8.00 m (4Н, 4-FС6Н4), 7.81 d (1Н,
Н2, J2,6 2.4 Hz), 9.58 s (1Н, NН), 10.78 s (1Н, ОН).
19F NMR spectrum, δ, ppm: –105.36 s (4-FС6Н4). Found,
%: N 4.00, 4.02. C13H12FNO5S2. Calculated, %: N 4.06.
anesulfonamide (IVk). Yield 91%, mp 189–191°С.
1Н NMR spectrum, δ, ppm: 2.06 s (3Н, 3-Mе), 2.23 s
(3Н, 2-Mе), 2.37 s (3Н, Mе in Ts), 2.95 s (3Н, MеSO2),
7.40 d (2Н, Н3',5', Ts, J 8.4 Hz), 7.68 s (1Н, Н6), 7.79 d
(2Н, Н2',6', Ts, J 8.4 Hz), 9.15 br.s (1Н, NН), 9.65 br.s
(1Н, ОН). Found, %: N 3.71, 3.77. C16H19NO5S2. Cal-
culated, %: N 3.79.
N-[4-Hydroxy-2,3-dimethyl-5-(4-chlorophenyl-
sulfonyl)phenyl]methanesulfonamide (IVl). Yield
75%, mp 196–198°С. 1Н NMR spectrum, δ, ppm: 2.06 s
(3Н, 3-Mе), 2.24 s (3Н, 2-Mе), 2.97 s (3Н, MеSO2),
7.69 d (2Н, Н3',5', 4-ClС6Н4, J 9.0 Hz), 7.70 s (1Н,
Н6), 7.90 d (2Н, Н2',6', 4-ClC6H4, J 9.0 Hz), 9.18 br.s
(1Н, NН), 9.77 br.s (1Н, ОН). Found, %: N 3.51, 3.55.
C15H16ClNO5S2. Calculated, %: N 3.59.
N-[4-Hydroxy-3-(trifluoromethylsulfonyl)phenyl]
methanesulfonamide (IVf). Yield 91%, mp 75–78°С.
1Н NMR spectrum, δ, ppm: 2.95 s (3Н, MеSO2),
7.15 d (1Н, Н5, J5.6 8.7 Hz), 7.60 d.d (1Н, Н6, J6,5 8.7,
J6,2 2.4 Hz), 7.67 d (1Н, Н2, J2,6 2.4 Hz), 9.75 s (1Н,
NН), 11.71 s (1Н, ОН). 19F NMR spectrum, δ, ppm:
–76.70 с (CF3). Found, %: N 4.34, 4.37. C8H8F3NO5S2.
Calculated, %: N 4.39.
N-[4-Hydroxy-3,6-dimethyl-5-tosylphenylmeth-
anesulfonamide (IVm). Yield 87%, mp 183–186°С.
1Н NMR spectrum, δ, ppm: 2.20 s (3Н, Mе in Ts), 2.33 s
(3Н, 3-Mе), 2.40 s (3Н, 6-Mе), 2.95 s (3Н, MеSO2),
7.41 s (1Н, Н2), 7.45 d (2Н, Н3',5', Ts, J 8.1 Hz), 7.78 d
(2Н, Н2',6', Ts, J 8.1 Hz), 9.02 s (1Н, NН), 10.45 br.s (1Н,
ОН). Found, %: N 3.75, 3.79. C16H19NO5S2. Calculated,
%: N 3.79.
N-[4-Hydroxy-3-methyl-5-(4-methoxyphenylsul-
fonyl)phenyl]methanesulfonamide (IVg). Yield 92%,
mp 134–135°С. 1Н NMR spectrum, δ, ppm: 2.13 s (3Н,
3-Mе), 2.95 s (3Н, MеSO2), 3.83 s (3Н, MеО), 7.12 d
(2Н, Н3',5', 4-MеОС6Н4, J 8.4 Hz), 7.25 d (1Н, Н2,
J2,6 2.1 Hz), 7.66 d (1Н, Н6, J6,2 2.1 Hz), 7.84 d (2Н,
Н2',6', 4-MеОС6Н4, J 8.4 Hz), 9.58 br.s (1Н, NН). Found,
%: N 3.79, 3.83. C15H17NO6S2. Calculated, %: N 3.77.
N-[4-Hydroxy-3,6-dimethyl-5-(4-chlorophenylsul-
fonyl)phenyl]methanesulfonamide (IVn). Yield 90%,
mp 155–157°С. 1Н NMR spectrum, δ, ppm: 2.42 s (3Н,
3-Mе), 2.55 s (3Н, 6-Mе), 2.96 s (3Н, MеSO2), 7.40 s (1Н,
Н2), 7.71 d (2Н, Н3',5', 4-ClС6Н4, J 8.1 Hz), 7.90 d (2Н,
Н2',6', 4-ClС6Н4, J 8.1 Hz), 9.06 s (1Н, NН), 10.19 br.s
(1Н, ОН). Found, %: N 3.55, 3.57. C15H16ClNO5S2.
Calculated, %: N 3.59.
N-[4-Hydroxy-3-methyl-5-(4-fluorophenylsulfonyl)
phenyl]methanesulfonamide (IVh). Yield 91%, mp
1
176–178°С. Н NMR spectrum, δ, ppm: 2.09 s (3Н,
3-Mе), 2.95 s (3Н, MеSO2), 7.23 d (1Н, Н2, J2,6 2.1 Hz),
7.37–7.99 m (4Н, 4-FС6Н4), 7.65 d (1Н, Н6, J6,2 2.1 Hz),
9.50 br.s (1Н, NН). 19F NMR spectrum, δ, ppm: –105.49 s
(4-FС6Н4). Found, %: N 3.83, 3.87. C14H14FNO5S2.
Calculated, %: N 3.90.
N-[4-Hydroxy-2,6-dimethyl-5-(4-methoxyphenyl-
sulfonyl)phenyl]methanesulfonamide (IVo). 1Н NMR
spectrum, δ, ppm: 2.28 s (3Н, 6-Mе), 2.59 s (3Н, 2-Mе),
3.03 s (3Н, MеSO2), 3.83 s (3Н, MеО), 6.69 s (1Н, Н3),
7.12 d (2Н, Н3',5', 4-MеОС6Н4, J 9.0 Hz), 7.82 d (2Н,
Н2',6', 4-MеОС6Н4, J 9.0 Hz), 8.84 s (1Н, NН), 10.54 s
(1Н, ОН).
N-[4-Hydroxy-2-methyl-5-tosylphenyl]methane-
sulfonamide (IVi). Yield 70%, mp 187–189°С. 1Н NMR
spectrum, δ, ppm: 2.26 s (3Н, 2-Mе), 2.36 s (3Н, Ts),
2.97 s (3Н, MеSO2), 6.76 s (1Н, Н3), 7.38 d (2Н, Н3',5', Ts,
J 7.8 Hz), 7.76 s (1Н, Н6), 7.77 d (2Н, Н2',6', Ts, J 7.8 Hz),
9.09 s (1Н, NН), 10.79 s (1Н, ОН). Found, %: N 3.85,
3.89. C15H17NO5S2. Calculated, %: N 3.94.
N-[4-Hydroxy-2,6-dimethyl-5-(4-fluorophenylsul-
1
N-[4-Hydroxy-2-methyl-5-(4-chlorophenylsulfo-
nyl)phenyl]methanesulfonamide (IVi). Yield 90%,
mp 210–212°С. 1Н NMR spectrum, δ, ppm: 2.28 s (3Н,
2-Mе), 2.99 s (3Н, MеSO2), 6.78 s (1Н, Н3), 7.68 d (2Н,
Н3',5', 4-ClС6Н4, J 8.4 Hz), 7.77 s (1Н, Н6), 7.90 d (2Н,
Н2',6', 4-ClС6Н4, J 8.4 Hz), 9.11 s (1Н, NН), 10.94 s (1Н,
ОН). Found, %: N 3.75, 3.77. C14H14ClNO5S2. Calcu-
lated, %: N 3.73.
fonyl)phenyl]methanesulfonamide (IVp). Н NMR
spectrum, δ, ppm: 2.30 s (3Н, 6-Mе), 2.66 s (3Н, 2-Mе),
3.04 s (3Н, MеSO2), 6.66 s (1Н, Н3), 7.38–7.97 m (4Н,
4-FC6H4), 8.87 s (1Н, NН), 10.64 с (1Н, ОН). 19F, δ,
ppm: –102.74 s (4-FС6Н4).
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)
phenyl]-1,1,1-trifluoromethanesulfonamide (Vа).
Yield 60%, mp 166–167°С. 1Н NMR spectrum, δ, ppm:
3.87 s (3Н, MеО), 7.00 d (1Н, Н5, J5,6 8.7 Hz), 7.15 d
N-(4-Hydroxy-2,3-dimethyl-5-tosylphenyl)-meth-
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AVDEENKO et al.
230
(2Н, Н3',5', 4-MеОС6Н4, J 8.7 Hz), 7.40 d.d (1Н, Н6,
J6,5 8.7 Hz, J6,2 1.8 Hz), 7.81 d (1Н, Н2, J2,6 1.8 Hz),
7.86 d (2Н, Н2',6', 4-MеОC6H4, J 8.7 Hz), 11.11 s (1Н,
NН), 11.89 br.s (1Н, ОН). 19F NMR spectrum, δ, ppm:
–75.26 s (CF3). Found, %: N 3.38, 3.39. C14H12F3NO6S2.
Calculated, %: N 3.40.
N-[4-Hydroxy-3-methyl-5-(4-chlorophenylsulfo-
nyl)phenyl]-1,1,1-trifluoromethanesulfonamide (Vg).
Yield 60%, mp 167–170°С. 1Н NMR spectrum, δ, ppm:
2.16 s (3Н, 3-Mе), 7.33 br.s (1Н, Н2), 7.68 br.s (1Н, Н6),
7.69 d (2Н, Н3',5', 4-ClС6Н4, J 8.4 Hz), 7.90 d (2Н, Н2',6'
,
4-ClС6Н4, J 8.4 Hz), 10.14 s (1Н, NН). 19F NMR spec-
trum, δ, ppm: –75.03 s (CF3). Found, %: N 3.20, 3.27.
C14H11ClF3NO5S2. Calculated, %: N 3.26.
N-[4-Hydroxy-3-tosylphenyl]-1,1,1-trifluorometh-
anesulfonamide (Vb). Yield 61%, mp 149–151°С.
1Н NMR spectrum, δ, ppm: 2.42 s (3Н, Mе in Ts),
6.99 d (1Н, Н5, J5,6 8.7 Hz), 7.42 d.d (1Н, Н6, J6,5 8.7,
J6,2 1.2 Hz), 7.43 d (2Н, Н3',5', Ts, J 6.9 Hz), 7.80 d (2Н,
Н2',6', Ts, J 6.9 Hz), 7.82 d (1Н, Н2, J2,6 1.2 Hz), 11.14 s
(1Н, NН). 19F NMR spectrum, δ, ppm: –75.01 s (CF3).
Found, %: N 3.51, 3.55. C14H12F3NO5S2. Calculated,
%: N 3.54.
N-[4-Hydroxy-2-methyl-5-(4-chlorophenylsulfo-
nyl)phenyl]-1,1,1-trifluoromethanesulfonamide (Vh).
Yield 63%, mp 163–165°С. 1Н NMR spectrum, δ, ppm:
2.28 s (3Н, 2-Mе), 6.84 s (1Н, Н3), 7.69 d (2Н, Н3',5'
4-ClС6Н4, J 8.4 Hz), 7.74 s (1Н, Н6), 7.90 d (2Н, Н2',6'
,
,
4-ClС6Н4, J 8.4 Hz), 11.22 s (1Н, NН). 19F NMR spec-
trum, δ, ppm: –75.99 s (CF3). Found, %: N 3.21, 3.29.
C14H11ClF3NO5S2. Calculated, %: N 3.26.
N-[4-Hydroxy-3-(phenylsulfonyl)phenyl]-1,1,1-
trifluoromethanesulfonamide (Vc). Yield 91%, mp
N-[4-Hydroxy-2,3-dimethyl-5-tosylphenyl]-
1,1,1-trifluoromethanesulfonamide (Vi). Yield 90%,
mp 170–173°С. 1Н NMR spectrum, δ, ppm: 2.13 s (3Н,
3-Mе), 2.27 s (3Н, 2-Mе), 2.43 s (3Н, Mе in Ts), 7.45 d
(2Н, Н3',5', Ts, J 8.4 Hz), 7.69 s (1Н, Н6), 7.82 d (2Н,
Н2',6', Ts, J 8.4 Hz), 9.91 s (1Н, NН), 11.60 br.s (1Н, ОН).
19F NMR spectrum, δ, ppm: –75.79 s (CF3). Found, %:
N 3.25, 3.29. C16H16F3NO5S2. Calculated, %: N 3.31.
1
137–139°С. Н NMR spectrum, δ, ppm: 7.20 d (1Н,
Н5, J5,6 8.7 Hz), 7.63 d.d (1Н, Н6, J6,5 8.7, J6,2 1.2 Hz),
7.82–8.15 m (5Н, Ph), 8.05 d (1Н, Н2, J2,6 1.2 Hz),
11.32 s (1Н, NН), 12.08 br.s (1Н, ОН). 19F NMR spec-
trum, δ, ppm: –75.04 s (CF3). Found, %: N 3.63, 3.67.
C13H10F3NO5S2. Calculated, %: N 3.67.
N-[4-Hydroxy-3-(4-chlorophenylsulfonyl)phenyl]-
1,1,1-trifluoromethanesulfonamide (Vd). Yield 82%,
mp 168–169°С. 1Н NMR spectrum, δ, ppm: 6.98 d (1Н,
Н5, J5,6 7.8 Hz), 7.43 d.d (1Н, Н6, J6,5 7.8, J6,2 1.2 Hz),
7.70 d (2Н, Н3',5', 4-ClС6Н4, J 8.7 Hz), 7.81 br.s (1Н,
Н2, J2,6 1.2 Hz), 7.90 d (2Н, Н2',6', 4-ClС6Н4, J 8.7 Hz),
11.27 s (1Н, NН), 12.04 br.s (1Н, ОН). 19F NMR spec-
trum, δ, ppm: –74.93 s (CF3). Found, %: N 3.41, 3.44.
C13H9ClF3NO5S2. Calculated, %: N 3.37.
N-[4-Hydroxy-2,3-dimethyl-5-(4-chlorophenyl-
sulfonyl)phenyl]-1,1,1-trifluoromethanesulfonamide
(Vj). Yield 92%, mp 198–200°С. 1Н NMR spectrum, δ,
ppm: 2.09 s (3Н, 3-Mе), 2.24 s (3Н, 2-Mе), 7.68 s (1Н,
Н6), 7.69 d (2Н, Н3',5', 4-ClС6Н4, J 8.4 Hz), 7.88 d (2Н,
Н2',6', 4-ClС6Н4, J 8.4 Hz), 10.07 s (1Н, NН), 11.67 br.s
(1Н, ОН). 19F NMR spectrum, δ, ppm: –75.89 s (CF3).
Found, %: N 3.10, 3.12. C15H13ClF3NO5S2. Calculated,
%: N 3.16.
N-[4-Hydroxy-3-(4-fluorophenylsulfonyl)phenyl]-
1,1,1-trifluoromethanesulfonamide (Ve). Yield 59%,
N-[4-Hydroxy-3,6-dimethyl-5-(4-methoxyphenyl-
sulfonyl)phenyl]-1,1,1-trifluoromethanesulfonamide
(Vk). Yield 91%, mp 165–168°С. 1Н NMR spectrum, δ,
ppm: 2.22 s (3Н, 3-Mе), 2.33 s (3Н, 6-Mе), 3.89 s (3Н,
MеО), 7.21 d (2Н, Н3',5', 4-MеОС6Н4, J 8.4 Hz), 7.36
s (1Н, Н2), 7.85 d (2Н, Н2',6', 4-MеОС6Н4, J 8.4 Hz),
10.55 s (1Н, NН). 19F NMR spectrum, δ, ppm: –76.13 s
(CF3). Found, %: N 3.13, 3.19. C16H16F3NO6S2. Calcu-
lated, %: N 3.19.
1
mp 189–191°С. Н NMR spectrum, δ, ppm: 6.98 d
(1Н, Н5, J5,6 8.7 Hz), 7.39–7.44 d.d (1Н, Н6, J6,5 8.7,
J6,2 1.2 Hz), 7.43–7.99 m (4Н, 4-FС6Н4), 7.79 d (1Н,
Н2, J2,6 1.2 Hz), 11.24 s (1Н, NН). 19F NMR spectrum,
δ, ppm: –74.84 s (CF3), –104.51 s (4-FС6Н4). Found,
%: N 3.51, 3.55. C13H9F4NO5S2. Calculated, %: N 3.51.
N-[4-Hydroxy-3-(trifluoromethylsulfonyl)phenyl]-
1,1,1-trifluoromethanesulfonamide (Vf). Yield 66%,
mp 87–89°С. 1Н NMR spectrum, δ, ppm: 7.20 d (1Н, Н5,
N-[4-Hydroxy-3,6-dimethyl-5-tosylphenyl]-1,1,1-
trifluoromethanesulfonamide (Vl). Yield 78%, mp
J
5,6 9.0 Hz), 7.48 br.s (1Н, NН), 7.66 br.s (1Н, Н2), 7.67 d
1
(1Н, Н6, J6,5 9.0 Hz), 8.60 br.s (1Н, ОН). 19F NMR spec-
trum, δ, ppm: –75.75 s (CF3SO2NH), –79.48 s (CF3SO2).
Found, %: N 3.70, 3.73. C8H5F6NO5S2. Calculated, %:
N 3.75.
175–177°С. Н NMR spectrum, δ, ppm: 2.24 s (3Н,
3-Mе), 2.35 s (3Н, 6-Mе), 2.46 s (3Н, Mе in Ts), 7.39 s
(1Н, Н2), 7.49 d (2Н, Н3',5', Ts, J 7.5 Hz), 7.81 d (2Н,
Н2',6', Ts, J 7.5 Hz), 10.60 s (1Н, NН), 11.48 br.s (1Н,
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REACTIONS OF N-ARYL(METHYL,TRIFLUOROMETHYL)SULFONYL-1,4-BENZOQUINONE...
231
ОН). 19F NMR spectrum, δ, ppm: –76.13 с (CF3). Found,
%: N 3.24, 3.30. C16H16F3NO5S2. Calculated, %: N 3.31.
J 6.9 Hz), 3.18–3.27 m (2Н, 3,5-CHMе2), 3.62 s (3Н,
MеSO2), 3.86 s (3Н, MеО), 6.61 s (1Н, Н2,6), 7.16 d
(2Н, Н3',5', 4-MеОС6Н4, J 9.2 Hz), 7.70 d (2Н, Н2',6'
4-MеОС6Н4, J 9.2 Hz), 8.63 s (1Н, ОН).
,
N-[4-Hydroxy-2,6-dimethyl-5-(4-methoxyphenyl-
sulfonyl)phenyl]-1,1,1-trifluoromethanesulfonamide
(Vm). Yield 65%, mp 142–145°С. 1Н NMR spectrum, δ,
ppm: 2.27 s (3Н, 2-Mе), 2.59 s (3Н, 6-Mе), 3.85 s (3Н,
MеО), 6.74 s (1Н, Н3), 7.11 d (2Н, Н3',5', 4-MеОС6Н4,
J 9.0 Hz), 7.83 d (2Н, Н2',6', 4-MеОС6Н4, J 9.0 Hz),
10.78 s (1Н, NН), 11.34 br.s (1Н, ОН). 19F NMR spec-
trum, δ, ppm: –76.67 s (CF3). Found, %: N 3.24, 3.25.
C16H16F3NO6S2. Calculated, %: N 3.19.
N-(4-Hydroxy-3,5-diisopropylphenyl)-N-(4-
chlorophenylsulfonyl)methanesulfonamide (VIId).
1Н NMR spectrum, δ, ppm: 1.05 d (12Н, 3,5-CHMе2,
J 6.9 Hz), 3.18–3.25 m (2Н, 3,5-CHMе2), 3.66 s (3Н,
MеSO2), 6.63 s (1Н, Н2,6), 7.77 d (4Н, 4-ClC6H4,
J 8.4 Hz), 8.70 br.s (1Н, ОН).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N-(4-me-
thoxyphenylsulfonyl)methanesulfonamide (VIIe).
1Н NMR spectrum, δ, ppm: 1.24 br.s (18Н, 3,5-СMе3),
3.60 s (3Н, MеSO2), 3.86 s (3Н, MеО), 6.70 s (1Н,
Н2,6), 7.16 d (2Н, Н3',5', 4-MеОС6Н4, J 8.7 Hz), 7.70 d
(2Н, Н2',6', 4-MеОС6Н4, J 8.7 Hz), 9.78 s (1Н, ОН).
N-[4-Hydroxy-2,6-dimethyl-5-tosylphenyl]-1,1,1-
trifluoromethanesulfonamide (Vn). Yield 91%, mp
1
153–155°С. Н NMR spectrum, δ, ppm: 2.31 s (3Н,
2-Mе), 2.43 s (3Н, Mе in Ts), 2.63 s (3Н, 6-Mе), 6.77 s
(1Н, Н3), 7.43 d (2Н, Н3',5', Ts, J 8.1 Hz), 7.80 d (2Н,
Н2',6', Ts, J 8.1 Hz), 10.81 s (1Н, NН), 11.23 s (1Н, ОН).
19F NMR spectrum, δ, ppm: –76.41 s (CF3). Found, %:
N 3.34, 3.35. C16H16F3NO5S2. Calculated, %: N 3.31.
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N-(4-
chlorophenylsulfonyl)methanesulfonamide (VIIf).
1Н NMR spectrum, δ, ppm: 1.29 br.s (18Н, 3,5-СMе3),
3.65 s (3Н, MеSO2), 6.72 s (1Н, Н2,6), 7.76 br.s (4Н,
4-ClC6H4), 9.74 s (1Н, ОН).
N-(4-Hydroxy-2,6-dimethylphenyl)-N-(4-methoxy-
1
phenylsulfonyl)methanesulfonamide (VIа). Н NMR
spectrum, δ, ppm: 1.88 s (6Н, 2,6-Mе), 3.65 s (3Н,
MеSO2), 3.87 s (3Н, MеО), 6.48 s (1Н, Н3,5), 7.16 d
N-(4-Hydroxy-3,5-dimethylphenyl)-N-(4-
methoxyphenylsulfonyl)-1,1,1-trifluoromethane-
(2Н, Н3',5', 4-MеОС6Н4, J 8.4 Hz), 7.71 d (2Н, Н2',6'
4-MеОС6Н4, J 8.4 Hz), 9.73 s (1Н, ОН).
,
1
sulfonamide (VIIIа). Н NMR spectrum, δ, ppm:
2.16 s (6Н, 3,5-Mе), 3.77 s (MеО), 6.71 s (1Н, Н2,6),
7.17 d (2Н, Н3',5', 4-MеОС6Н4, J 8.4 Hz), 7.86 d (2Н,
Н2',6', 4-MеОС6Н4, J 8.4 Hz). 19F NMR spectrum, δ,
ppm: –75.83 s (CF3).
N-(4-Hydroxy-2,6-dimethylphenyl)-N-(4-fluoro-
phenylsulfonyl)methanesulfonamide (VIb). 1Н NMR
spectrum, δ, ppm: 1.90 s (6Н, 2,6-Mе), 3.66 s (3Н,
MеSO2), 6.50 s (1Н, Н3,5), 7.44 d (2Н, Н3',5', 4-FС6Н4,
J 8.4 Hz), 7.93 d (2Н, Н2',6', 4-FC6H4, J 8.4 Hz), 9.74 s
(1Н, ОН). 19F NMR spectrum, δ, ppm: –102.60 s (4-
FС6Н4).
N-(4-Hydroxy-3,5-dimethylphenyl)-N-tosyl-
1,1,1-trifluoromethanesulfonamide (VIIIb). 1Н NMR
spectrum, δ, ppm: 2.19 s (6Н, 3,5-Mе), 2.42 s (3Н, Mе
in Ts), 6.75 s (1Н, Н2,6), 7.33 d (2Н, Н3',5', Ts, J 8.4 Hz),
7.88 d (2Н, Н2',6', Ts, J 8.4 Hz). 19F NMR spectrum, δ,
ppm: –75.93 s (CF3).
N-(4-Hydroxy-3,5-dimethylphenyl)-N-(4-me-
thoxyphenylsulfonyl)methanesulfonamide (VIIа).
1Н NMR spectrum, δ, ppm: 2.12 s (6Н, 3,5-Mе), 3.54 s
(3Н, MеSO2), 3.88 s (3Н, MеО), 6.73 s (1Н, Н2,6), 7.17 d
N-[3,5-Dimethyl-4-(4-methoxyphenoxy)phenyl]
1
methanesulfonamide (IXа). Н NMR spectrum,
(2Н, Н3',5', 4-MеОС6Н4, J 9.3 Hz), 7.74 d (2Н, Н2',6'
4-MеОС6Н4, J 9.3 Hz), 8.81 s (1Н, ОН).
,
δ, ppm: 2.03 s (6Н, 3,5-Mе), 3.02 s (3Н, MеSO2),
3.90 s (3Н, MеО), 6.92 s (1Н, Н2,6), 7.24 d (2Н, Н3',5'
,
4-MеОС6Н4, J 9.0 Hz), 7.90 d (2Н, Н2',6', 4-MеОС6Н4,
J 9.0 Hz), 9.79 s (1Н, NН).
N-(4-Hydroxy-3,5-dimethylphenyl)-N-(4-chloro-
phenylsulfonyl)methanesulfonamide (VIIb). 1Н NMR
spectrum, δ, ppm: 2.14 s (6Н, 3,5-Mе), 3.58 s (3Н,
MеSO2), 6.79 s (1Н, Н2,6), 7.75 d (2Н, Н3',5', 4-ClС6Н4,
J 8.4 Hz), 7.84 d (2Н, Н2',6', 4-ClС6Н4, J 8.4 Hz), 8.86 s
(1Н, ОН).
N-[3,5-Dimethyl-4-(4-chlorophenoxy)phenyl]
methanesulfonamide (IXb). Yield 66%, mp 185–
187°С. 1Н NMR spectrum, δ, ppm: 2.04 s (6Н, 3,5-Mе),
3.03 s (3Н, MеSO2), 6.94 s (1Н, Н2,6), 7.82 d (2Н,
Н3',5', 4-ClС6Н4, J 8.4 Hz), 8.02 d (2Н, Н2',6', 4-ClС6Н4,
J 8.4 Hz), 9.82 s (1Н, NН). Found, %: N 3.63, 3.67.
C15H16ClNO5S2. Calculated, %: N 3.59.
N-(4-Hydroxy-3,5-diisopropylphenyl)-N-(4-
methoxyphenylsulfonyl)methanesulfonamide (VIIc).
1Н NMR spectrum, δ, ppm: 1.05 d (12Н, 3,5-CHMе2,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012

AVDEENKO et al.
232
3.16 s (3Н, MeSO2), 7.26 s (1Н, Н6), 7.70 d (2Н, Н3',5'
,
N-[3,5-Diisopropyl-4-(4-methoxyphenoxy)-phenyl]
methanesulfonamide (IXc). 1Н NMR spectrum, δ, ppm:
1.03 d (12Н, 3,5-CHMе2, J 6.9 Hz), 3.02 s (3Н, MеSO2),
3.02–3.10 m (2Н, 3,5-CHMе2), 3.90 s (3Н, MеО), 7.03
s (1Н, Н2,6), 7.24 d (2Н, Н3',5', 4-MеОС6Н4, J 8.3 Hz),
7.92 d (2Н, Н2',6', 4-MеОС6Н4, J 8.3 Hz), 9.79 с (1Н, NН).
4-ClС6Н4, J 7.8 Hz), 7.93 d (2Н, Н2',6', 4-ClС6Н4,
J 7.8 Hz), 8.96 s (1Н, NН), 9.49 s (1Н, ОН).
N-[4-Hydroxy-3,5-dimethyl-2-(4-methoxyphenyl-
sulfonyl)phenyl]-1,1,1-trifluoromethanesulfonamide
(XIIа). 1Н NMR spectrum, δ, ppm: 2.14 s (3Н, 5-Mе),
2.22 s (3Н, 3-Mе), 3.89 s (3Н, MеО), 7.03 s (1Н, Н6),
7.21 d (2Н, Н3',5', 4-MеОС6Н4, J 7.8 Hz), 7.89 d (2Н,
Н2',6', 4-MеОС6Н4, J 7.8 Hz), 9.24 s (1Н, NН), 11.43 s
(1Н, ОН). 19F NMR spectrum, δ, ppm: –75.34 s (CF3).
N-[3,5-Diisopropyl-4-(4-chlorophenoxy)phenyl]
methanesulfonamide (IXd). Yield 59%, mp 146–147°С.
1Н NMR spectrum, δ, ppm: 1.05 d (12Н, 3,5-CHMе2,
J 6.9 Hz), 2.94–3.03 m (2Н, 3,5-CHMе2), 3.03 s (3Н,
MеSO2), 7.03 s (1Н, Н2,6), 7.83 d (2Н, Н3',5', 4-ClС6Н4,
J 8.3 Hz), 8.04 d (2Н, Н2',6', 4-ClC6H4, J 8.3 Hz), 9.98 s
(1Н, NН). Found, %: N 3.08, 3.12. C19H24ClNO5S2.
Calculated, %: N 3.14.
N-(4-Hydroxy-3,5-dimethyl-2-tosylphenyl)-1,1,1-
1
trifluoromethanesulfonamide (XIIb). Н NMR spec-
trum, δ, ppm: 2.12 s (3Н, 5-Mе), 2.23 s (3Н, 3-Mе),
2.46 s (3Н, Mе in Ts), 7.04 s (1Н, Н6), 7.52 d (2Н, Н3',5'
,
Ts, J 7.8 Hz), 7.86 d (2Н, Н2',6', Ts, J 7.8 Hz), 9.31 s (1Н,
NН), 11.40 s (1Н, ОН). 19F NMR spectrum, δ, ppm:
–75.36 s (CF3).
N-[3,5-Di-tert-butyl-4-(4-methoxyphenoxy)phenyl]
methanesulfonamide (IXe). 1Н NMR spectrum, δ, ppm:
1.25 s (18Н, 3,5-СMе3), 3.03 s (3Н, MеSO2), 3.90 s (3Н,
MеО), 7.22 s (1Н, Н2,6), 7.24 d (2Н, Н3',5', 4-MеОС6Н4,
J 8.3 Hz), 7.92 d (2Н, Н2',6', 4-MеОС6Н4, J 8.3 Hz),
9.79 s (1Н, NН).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)methanesul-
fonamide (XIII), mp 139–141°С. 1Н NMR spectrum, δ,
ppm: 1.34 s (18Н, 3,5-CMe3), 2.82 s (3Н, MеSO2), 6.12 s
(2Н, Н2,6), 8.72 br.s (1Н, NН), 9.40 br.s (1Н, ОН). Found,
%: N 4.69, 4.72. C15H25NO3S. Calculated, %: N 4.68.
N-[3,5-Di-tert-butyl-4-(4-chlorophenoxy)phenyl]
methanesulfonamide (IXf). 1Н NMR spectrum, δ, ppm:
1.24 s (18Н, 3,5-СMе3), 3.01 s (3Н, MеSO2), 7.24 s (1Н,
Н2,6), 7.38 d (2Н, Н3',5', 4-ClС6Н4, J 8.3 Hz), 7.60 d (2Н,
Н2',6', 4-ClC6H4, J 8.3 Hz), 9.74 s (1Н, NН).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-1,1,1-
trifluoromethanesulfonamide (XIV), mp 106–109°С.
1Н NMR spectrum, δ, ppm: 1.38 s (18Н, 3,5-CMe3),
7.00 s (2Н, Н2,6), 7.19 br.s (1Н, NН), 11.32 br.s (1Н,
ОН). 19F NMR spectrum, δ, ppm: –75.11 s (CF3). Found,
%: N 3.93, 3.95. C15H22F3NO3S. Calculated, %: N 3.96.
N-[3,5-Dimethyl-4-(4-methoxyphenoxy)phenyl]-
1
1,1,1-trifluoromethanesulfonamide (Xа). Н NMR
spectrum, δ, ppm: 2.06 s (6Н, 3,5-Mе), 3.83 s (3Н,
MеО), 7.00 s (1Н, Н2,6), 7.11 d (2Н, Н3',5', 4-MеОС6Н4,
J 8.4 Hz), 7.78 d (2Н, Н2',6', 4-MеОС6Н4, J 8.4 Hz), 9.22 s
(1Н, NН). 19F NMR spectrum, δ, ppm: –75.70 s (СF3).
ACKNOWLEDGMENTS
The authors express their gratitude for the help in
performing the calculations and for supplying software to
the staff of the department ORSIKH GNU NTK “Institute
of Single Crystals” of the NationalAcademy of Sciences
of Ukraine and of the Ukrainian-American laboratory of
quantum chemistry (Kharkov, Ukraine, Jackson, USA).
N-[3,5-Dimethyl-4-(4-methylphenoxy)phenyl]-
1,1,1-trifluoromethanesulfonamide (Xb). Н NMR
spectrum, δ, ppm: 2.06 s (6Н, 3,5-Mе), 2.39 s (3Н, Mе
in Ts), 7.00 s (1Н, Н2,6), 7.39 d (2Н, Н3',5', Ts, J 8.1 Hz),
7.72 d (2Н, Н2',6', Ts, J 8.1 Hz), 9.22 s (1Н, NН). 19F NMR
spectrum, δ, ppm: –75.69 s (СF3).
1
N-[4-Hydroxy-3,5-dimethyl-2-(4-methoxyphenyl-
sulfonyl)phenyl]methanesulfonamide (XIа). 1Н NMR
spectrum, δ, ppm: 2.20 s (3Н, 5-Mе), 2.24 s (3Н, 3-Mе),
3.16 s (3Н, MеSO2), 3.85 s (3Н, MеО), 7.02 s (1Н, Н6),
7.29 d (2Н, Н3',5', 4-MеОС6Н4, J 7.8 Hz), 7.81 d (2Н,
Н2',6', 4-MеОС6Н4, J 7.8 Hz), 8.91 s (1Н, NН), 9.52 s
(1Н, ОН).
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REACTIONS OF N-ARYL(METHYL,TRIFLUOROMETHYL)SULFONYL-1,4-BENZOQUINONE...
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