Reactions of arylsulfinyl chlorides and N-(arylsulfonyl)arylsulfinimidoyl chlorides with p-aminophenols

Article abstract of DOI:10.1134/S1070428007100107

In reactions of arylsulfinyl chlorides and N-(arylsulfonyl) arylsulfinimidoyl chlorides with p-aminophenols formed N-arylthio-1,4- benzoquinone imines, evidently through a stage of N-arylsulfinyl-4-aminophenols and N-(N-arylsulfonyl)arylsulfinylimidoyl-4-aminophenols that under the reaction conditions eliminate respectively H₂O and ArSO₂NH ₂.

Full text of DOI:10.1134/S1070428007100107

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1471−1474. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, A.A. Santalova, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 10,
pp. 1479−1481.
Reactions of Arylsulfinyl Chlorides
and N-(Arylsulfonyl)arylsulfinimidoyl Chlorides
with p-Aminophenols
A. P. Avdeenko, S. A. Konovalova, and A. A. Santalova
Donbass State Machine-Building Academy, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
Received January 30, 2007
Abstract—In reactions of arylsulfinyl chlorides and N-(arylsulfonyl)arylsulfinimidoyl chlorides with
p-aminophenols formed N-arylthio-1,4-benzoquinone imines, evidently through a stage of N-arylsulfinyl-4-
aminophenols and N-(N-arylsulfonyl)arylsulfinylimidoyl-4-aminophenols that under the reaction conditions
eliminate respectively H2O and ArSO2NH2.
DOI: 10.1134/S1070428007100107
We thoroughly investigated formerly the structural
features and reactivity of N-aroyl-1,4-benzoquinone
monoimines I. N-(N-arylsulfonyl)arylimidoyl-1,4-benzo-
quinone monoimines II are their structural analogs with
a similar reactivity [1].
sulfinylimidoyl chlorides V [3]. Based on published data
we presumed a possible preparation of quinone imines
IV by reaction of N-(arylsulfonyl)arylsulfinylimidoyl
chlorides V with p-aminophenols VI with subsequent
oxidation of formed N-(N-arylsulfonyl)aryl-sulfinyl-
imidoyl-4-aminophenols A.
Recently we prepared for the first time N-arylsulfinyl-
1,4-benzoquinone monoimines III in reaction of aryl-
sulfinyl chlorides with alkyl-substituted p-aminophenols
in ethyl ether or dioxane followed by oxidation in situ
of the formed N-arylsulfinyl-4-aminophenols with silver
oxide or lead tetraacetate [2].
However in the reaction of N-(arylsulfonyl)-
arylsulfinylimidoyl chlorides Va–Vd with p-amino-
phenols VIa–VIh N-arylthio-1,4-benzoquinone
monoimines VIIa–VIIh–IXa–IXh were obtained
(Scheme 1). The reaction was carried out in ethyl ether,
dioxane in the presence of triethylamine, and in
pyridine. The best results were obtained in reactions
performed in pyridine.
In this study we attempted to synthesize structural
analogs of N-arylsulfinyl-1,4-benzoquinone monoimines
III, N-(N-arylsulfonyl)aryl-sulfinylimidoyl-1,4-benzo-
quinone monoimines IV. An extensive literature exists
on the synthesis and reactivity of N-(arylsulfonyl)aryl-
Evidently the formed in the reaction unstable com-
pound A, N-(N-arylsulfonyl)arylsulfinylimidoyl-4-
aminophenol, suffered arylsulfamide elimination as was
experimentally proved by isolating from the reaction
mixture also the corresponding arylsulfamides.
NSO2Ar'
O
Ar C
Ar C
Thus we discovered a new unusual preparation
method for N-arylthio-1,4-benzoquinone monoimines
VII–IX: as a result of an intramolecular redox process
the tetravalent sulfur in compound A is reduced into
bivalent, and the aminophenol moiety is oxidized to
quinone imine. Note the high purity of compounds
obtained and the absence of disulfide impurities which
are difficult to remove from N-arylthio-1,4-benzoquinone
monoimines in preparation by the other traditional
methods [4, 5].
N
O
O
N
O
I
II
NSO2Ar'
O
Ar
S
Ar S
N
O
N
IV
III
1471

AVDEENKO et al.
1472
Scheme 1.
R3
R4
S Cl
ArSO2N
+
H2N
OH
R2
R1
X
_
_
Vа Vd
VIа VIh
R4
R3
R3
R2
R4
O
N
S
X
S NH
OH
ArSO2N
_HCl
_ ArSO2NH2
R1
R2
R1
_
_
_
VIIа VIIh IXа IXh
А
X
V, Ar = Ph (a, b, c), 4-ClC6H4 (d); X = H (a), Cl (b), NO2 (c, d); VI–IX, R1 = R4 = Me, R2 = R3 = H (a); R1 = R4 = H,
R2 = R3 = Me (b); R1 = R3 = Me, R2 = R4 = H (c); R1 = i-Pr, R3 = Me, R2 = R4 = H (d); R1 = Me, R2 = R3 = R4 = H (e);
R2 = Me, R1 = R3 = R4 = H (f); R1 = R4 = Cl, R2 = R3 = H (g); R1 = Me, R3 = i-Pr, R2 = R4 = H (h); X = H (VII), Cl (VIII),
NO2 (IX).
Scheme 2.
R3
R2
R4
R1
O
O
_
_
_
+ VIа VIh
X
S
OH
VIIа VIIh, IXа IXh
X
S NH
_H2O
_HCl
Cl
Xа, Xb
B
X = H (a), NO2 (b).
A similar intramolecular redox process occurs also
with N-arylsulfinyl-4-aminophenols B when the reaction
of arylsulfinyl chlorides with p-aminophenols is carried
out not in ethyl ether or dioxane but in pyridine
(Scheme 2). In this event unstable compound B elimin-
ates an H2O molecule and undergoes the intramolecular
redox process involving tetravalent sulfur reduction into
bivalent and aminophenol moiety oxidation into quinone
imine.
Thus the investigation performed established that in
reactions of p-aminophenols with arylsulfinyl chlorides
and N-(aryl-sulfonyl)arylsulfinylimidoyl chlorides first
formed the corresponding unstable N-arylsulfinyl-4-
aminophenols and N-(N-arylsulfonyl)arylsulfinyl-
imidoyl-4-aminophenols which we failed to isolate in
the individual state. Then an intramolecular redox process
occurred involving water or arylsulfamide elimination
leading to the formation of N-arylthio-1,4-benzoquinone
imines.
N-arylthio-1,4-benzoquinone imines VIIa–VIId,
VIIg, VIIh, VIIIa–VIIIh, IXa, IXb, and IXg obtained
were identical to those described in publications [4–6].
The structure of newly prepared quinone imines VIIe,
VIIf, IXc–IXf, and IXh was proved by elemental
EXPERIMENTAL
1H NMR spectra were registered on a spectrometer
Varian VXR-300 at operating frequency 300 MHz from
solutions in deuterochloroform, internal reference TMS.
1
analyses and H NMR spectra.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

REACTIONS OF ARYLSULFINYL CHLORIDES
1473
TLC was carried out on Silufol UV-254 plates using
chloroform as solvent, eluent benzene–hexane, 10:1,
spots visualized under UV irradiation.
N-4-Nitrophenylthio-2-methyl-1,4-benzoquinone
imine (IXe). Yield 53%, mp 161–163°C. 1H NMR
spectrum, δ, ppm, Z-isomer (38%): 7.78–8.32 d.d (4H,
Ar, Jo 9.3 Hz), 7.37–7.41 d.d [1H, H5, J(H3,5) 3.0,
J(H5,6) 10.2 Hz], 7.08 q (1H, H3), 6.62 d [1H, H6, J(H5,6)
9.6 Hz], 2.07 d (3H, C2H3, J 1.2 Hz); Ε-isomer (62%):
7.78–8.32 d.d (4H, Ar, Jo 9.3 Hz), 7.12–7.17 d.d [1H,
H5, J(H3,5) 3.0, J(H5,6) 9.9 Hz], 7.28 q (1H, H3), 6.55 d
[1H, H6, J(H5,6) 9.9 Hz], 2.12 d (3H, C2H3, J 1.5 Hz).
Found, %: N 10.07, 10.24; S 11.69, 11.83. C13H10N2O3S.
Calculated, %: N 10.21; S 11.69.
N-Arylthio-1,4-benzoquinone imines VIIa–VIIh–
IXa–IXh. To a dispersion of 2 mmol of p-aminophenol
VIa–VIh in 20 ml of anhydrous ethyl ether was added
an equimolar quantity of the corresponding arylsulfinyl
chloride and triethylamine. The separated precipitate of
triethylamine hydrochloride was filtered off, the filtrate
was evaporated under a vacuum of a water-jet pump.
The precipitate obtained was washed with methanol and
glacial acetic acid, and recrystallized from the glacial
acetic acid or hexane.
N-4-Nitrophenylthio-3-methyl-1,4-benzoquinone
1
imine (IXf). Yield 56%, mp 164–165°C. H NMR
spectrum, δ, ppm: 7.76–8.33 d.d (4H, Ar, JO 9.0 Hz),
7.38 d [1H, H5, J(H5,6) 10.2 Hz], 6.53–6.57 d.d [1H, H6,
J(H2,6) 2.1, J(H5,6) 10.2 Hz], 6.45 q (1H, H2), 2.32 d
(3H, C3H3, J 1.2 Hz). Found, %: N 10.07, 10.20; S 11.58,
11.72. C13H10N2O3S. Calculated, %: N 10.21; S 11.69.
The characteristics of quinone imines VIIa, VIIb–
IXa, IXb are published in [5], those of VIIc, VIId, VIIh,
VIIIa–VIIIf, and VIIIh in [6], VIIg–IXg in [4].
N-Phenylthio-2-methyl-1,4-benzoquinone imine
1
(VIIe). Yield 52%, mp 116–118°C. H NMR spectrum,
N-4-Nitrophenylthio-5-isopropyl-2-methyl-1,4-
benzoquinone imine (IXh). Yield 65%, mp 155–157°C.
1H NMR spectrum, δ, ppm: 7.75–8.33 d.d (4H, Ar, Jo
9.0 Hz), 7.22 d (1H, H3, J 1.5 Hz), 6.40 q (1H, H6), 3.41–
3.50 m (1H, CH in i-Pr), 2.09 d (3H, C2H3, J 1.5 Hz),
1.24 d (6H, Me in i-Pr, J 6.9 Hz). Found, %: N 8.71,
8.96; S 10.10, 10.26. C16H16N2O3S. Calculated, %: N
8.85; S 10.13.
δ, ppm, Z-isomer (32%): 7.30–7.64 m (5H, Ph), 7.39–
7.43 d.d [1H, H5, J(H3,5) 3.0, J(H5,6) 9.9 Hz], 7.01 q (1H,
H3), 6.56 d [1H, H6, J(H5,6) 9.9 Hz], 2.03 d (3H, C2H3,
J 1.5 Hz); Ε-isomer (68%): 7.30–7.64 m (5H, Ph), 7.06–
7.10 d.d [1H, H5, J(H3,5) 3.0, J(H5,6) 9.9 Hz], 7.30 q (1H,
H3), 6.49 d [1H, H6, J(H5,6) 9.6 Hz], 2.09 d (3H, C2H3,
J 1.2 Hz). Found, %: N 6.08, 6.10; S 13.92, 14.01.
C13H11NOS. Calculated, %: N 6.11; S 13.98.
Reaction of p-aminophenols VIa–VIh with
arylsulfinyl chlorides and N-(arylsulfonyl)aryl-
sulfinylimidoyl chlorides. a. To a solution of 1 mmol
of p-aminophenol VIa–VIh in 2 ml of pyridine was added
1 mmol of an appropriate arylsulfinyl chloride Xa or Xb
or N-(arylsulfonyl)arylsulfinylimidoyl chloride Va or Vd.
The solution was heated at 60–70°C. After 30 min the
reaction mixture was cooled and poured on ice mixed
with HCl. The arising oily substance crystallized on addi-
tion of a little AcOH. The formed precipitate of N-aryl-
thio-1,4-benzoquinone imines VIIa–VIIh–IXa–IXh was
recrystallized from acetic acid. The N-arylthio-1,4-
benzoquinone imines obtained were identical to known
N-Phenylthio-3-methyl-1,4-benzoquinone imine
(VIIf). Yield 61%, mp 124–125°C. 1
H NMR spectrum,
δ, ppm: 7.30–7.63 m (5H, Ph), 7.40 d [1H, H5, J(H5,6)
10.2 Hz], 6.47–6.51 d.d [1H, H6, J(H2,6) 1.8, J(H5,6)
9.9 Hz], 6.39 q (1H, H2), 2.26 d (3H, C3H3, J 1.2 Hz).
Found, %: N 6.01, 6.08; S 13.74, 13.97. C13H11NOS.
Calculated, %: N 6.11; S 13.98.
N-4-Nitrophenylthio-2,5-dimethyl-1,4-benzo-
quinone imine (IXc). Yield 60%, mp 224–225°C.
1H NMR spectrum, δ, ppm: 7.75–8.32 d.d (4H, Ar,
JO 9.0 Hz), 7.19 d (1H, H3), 6.42 q (1H, H6), 2.29 d (3H,
C5H3, J 1.2 Hz), 2.09 d (3H, C2H3, J 1.5 Hz). Found, %:
N 9.60, 9.78; S 11.08, 11.25. C14H12N2O3S. Calculated,
%: N 9.72; S 11.12.
1
authentic compounds (the same H NMR spectra and
mp, no mp depression on mixing with authentic samples).
N-4-Nitrophenylthio-6-isopropyl-3-methyl-1,4-
benzoquinone imine (IXd). Yield 57%, mp 154–155°C.
1H NMR spectrum, δ, ppm: 7.76–8.32 d.d (4H, Ar, JO
9.0 Hz), 7.09 d (1H, H5), 6.41 q (1H, H2), 3.07–3.16 m
(1H, CH in i-Pr), 2.29 d [3H, C3H3, J 0.9 Hz], 1.18 d
(6H, Me in i-Pr, J 6.9 Hz). Found, %: N 8.71, 8.86;
S 10.01, 10.16. C16H16N2O3S. Calculated, %: N 8.85;
S 10.13.
b. To a solution of 1 mmol of p-aminophenol VIa–
VIc, VIe, and VIh in 5 ml of dioxane were added at
room temperature equimolar amounts of N-(aryl-
sulfonyl)arylsulfinylimidoyl chlorides Va–Vd and
triethylamine.After 30 min 20–25 ml of water was added
to the reaction mixture. The arising oily substance
crystallized on addition of a little AcOH. The formed
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

AVDEENKO et al.
1474
Seleznenko, L.V., Zh. Org. Khim., 1966, vol. 2, p. 92;
Dubinina, T.N., Markovskii, L.N., and Levchenko, E.S.,
Zh. Org. Khim., 1977, vol. 13, p. 1621; Markovskii, L.N.,
Dubinina, T.N., Levchenko, E.S., and Kirsanov, A.V., Zh.
Org. Khim., 1971, vol. 7, p. 1547.
precipitate of N-arylthio-1,4-benzoquinone imines VIIa,
VIIIa, IXa–IXc, IXe, and IXh was recrystallized from
acetic acid.
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