Comparison of preparation methods of N-arylsulfinyl-1,4-benzoquinone monoimines

Article abstract of DOI:10.1134/s1070428008020085

Advantages and shortcomings were discussed of three procedures for preparation N-arylsulfinyl-1,4-benzoquinone imines: the reaction of arenesulfenyl chlorides with 1,4-benzoquinone oximes, the oxidation of N-arylthio-1,4-benzoquinone imines, and the reaction of arylsulfinyl chlorides with p-aminophenols followed by oxidation. A series of new N-arylsulfinyl-1,4- benzoquinone imines was obtained.

Full text of DOI:10.1134/s1070428008020085

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 2, pp. 231−236. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, A.A. Santalova, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 2,
pp. 240−245.
Comparison of Preparation Methods
of N-Arylsulfinyl-1,4-benzoquinone Monoimines
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 May 11, 2007
Abstract—Advantages and shortcomings were discussed of three procedures for preparation N-arylsulfinyl-1,4-
benzoquinone imines: the reaction of arenesulfenyl chlorides with 1,4-benzoquinone oximes, the oxidation of
N-arylthio-1,4-benzoquinone imines, and the reaction of arylsulfinyl chlorides with p-aminophenols followed by
oxidation. A series of new N-arylsulfinyl-1,4-benzoquinone imines was obtained.
DOI: 10.1134/S1070428008020085
Stable N-arylsulfinyl-1,4-benzoquinone monoimines
containing sulfur(IV) were formerly prepared by acyla-
tion of 1,4-benzoquinone monooximes with correspond-
ing arenesulfenyl chlorides (method a) [1]. In [2, 3]
a method of the synthesis of N-aryl(alkyl)sulfinyl-1,4-
benzoquinone monoimines by oxidation of N-aryl(alkyl)-
thio-1,4-benzoquinone imines with m-chloroperbenzoic
acid was described (method b). The traditional and the
most widely applied method of N-substituted 1,4-benzo-
quinone imines preparation is the oxidation of the
corresponding N-substituted p-aminophenols [4]. The
latter are as a rule obtained by reaction of the chlorides
of the corresponding acids with p-aminophenols.
Reactions were reported of arylsulfinyl chlorides with
various aromatic amines giving arylsulfinylamides [5].
Several preparative procedures for arylsulfinyl chlorides
were published [6]. Some N-arylsulfinyl-1,4-benzo-
quinone imines were produced by acylation of
p-aminophenols followed by oxidation with Pb(OAc)4
or Ag2O [7] (method c).
suitable solvent. This method is acceptable for prepara-
tion of any N-arylsulfinyl-1,4-benzoquinone imines, but
the substances obtained require repeated recrystalliza-
tion. The yields of reaction products were low (30–45%)
except for benzoquinone imines XIVe and XVIe whose
yields attained 65–70%. This method should not be used
with 4-methoxyphenylsulfenylchloride due to the
extremely low stability of the arising quinone imine.
In the synthesis of N-arylsulfinyl-1,4-benzoquinone
monoimines by method b special requirements are
presented to the purity of initial N-arylthio derivatives
for in the presence of insignificant impurities the reaction
product after oxidation is difficult to obtain in the
individual state even after multiple recrystallizations.
The case in point is diaryl disulfides that are very difficult
to remove from the target compounds. The most suitable
procedure for removal of the diaryl disulfide impurity is
the reaction of arylthiols with N-chloro-1,4-benzo-
quinone monoimines [8].
As oxidant in method b is used a mild reagent m-
chloroperbenzoic acid. In the reaction it is reduced to
m-chlorobenzoic acid that is easily removed from the
reaction mixture by washing with 10% water solution
of sodium hydrogen carbonate. The oxidant should be
applied to the reaction mixture by small portions,and
the reaction progress should be monitored by TLC.
The target of the present study was synthesis of new
N-arylsulfinyl-1,4-benzoquinone monoimines by the
above cited methods and revealing their advantages and
shortcomings in the preparation of certain N-arylsulfinyl-
1,4-benzoquinone monoimines (see the scheme).
At application of method a to the synthesis of N-
arylsulfinyl-1,4-benzoquinone monoimines a special
attention should be paid to the temperature regime of the
reaction (–10°C) and also to the quality of the solvent.
The dried and distilled ethyl ether proved to be the most
In preparation of quinone imines VIIa–VIIe, VIIIe,
and IXc–IXe by this method it was difficult to achieve
a complete consumption of the initial thioquinone imine.
The increased quantity of the oxidant resulted in the
231

AVDEENKO et al.
232
R1
+
X
SCl HON
O
à
R2
IIà–IIg
R3
Ià–Ie
R1
R1
O
S
m-ClC6H4C(O)OOH
X
S N
O
X
N
O
b
R2
R3
R2
R3
IIIà–IIIe – VIIa–VIIe, VIIIe, IXc–IXe
XIIà–XIIe – XVIa–XVIe, XVIIe,
XVIIIc–XVIIIe
R1
O
[O]
c
+
OH
H2N
X
S
Cl
R2
R3
XIà–XIg
Xà–Xg
I, III–X, XII–XVIII: X = MeO (a), Me (b), H (c), Cl (d), NO2 (e); II, XI: R1 = R2 = R3 = H (a), R2 = Me, R1 = R3 = H (b),
R1 = R2 = Me, R3 = H (c), R1 = R3 = Me, R2 = H (d), R1 = R2 = t-Bu, R3 = H (e), R1 = R2 = i-Pr, R3 = H (f), R1 = R2 = Cl, R3 =
H (g); III, XII: R1 = R2 = R3 = H; IV, XIII: R2 = Me, R1 = R3 = H; V, XIV: R1 = R2 = Me, R3 = H; VI, XV: R1 = R3 = Me,
R2 = H; VII, XVI: R1 = R2 = t-Bu, R3 = H; VIII, XVII: R1 = R2 = i-Pr, R3 = H; IX, XVIII: R1 = R2 = Cl, R3 = H.
formation of the corresponding N-arylsulfonyl derivative
[2]. Frequently three products are present simultaneously
in the reaction mixture: N-arylthio-, N-arylsulfinyl-, and
N-arylsulfonyl-1,4-benzoquinone monoimines. This may
result from the close values of the oxidation rate of these
compounds and also by the operation of a redox dis-
proportionation process of N-arylsulfinyl-1,4-benzo-
quinone monoimines.
ring compounds (XIIa–XIIe–XVa–XVe). The yield of
reaction products reach 65–85%.
In preparation of N-arylsulfinyl-1,4-benzoquinone
monoimines by method c the solvent for the reaction
significantly affects the course of the process.
It was shown formerly that the reaction of arylsulfinyl
chlorides Xa–Xe with p-aminophenols XIa–XIg carried
out in pyridine led to the formation of N-arylthio-1,4-
benzoquinone monoimines. The intermediate unstable
N-arylsulfinyl-4-aminophenols formed in this reaction
eliminate an H2O molecule and suffer an intramolecular
oxidation-reduction process resulting in transformation
of sulfur (IV) into sulfur(II), and the aminophenol moiety
into quinone imine [10].
The redox potential of N-arylthioquinone imines is
significantly more negative that the potential of the
corresponding N-arylsulfonyl-1,4-benzoquinone mono-
imines [9], and intermediate value corresponds to the
N-arylsulfinyl derivatives, as shows the result of oxida-
tion of N-arylthioquinone imines with 1 equiv of oxidant
to N-arylsulfinyl derivatives and with 2 equiv of oxidant,
to N-arylsulfonyl compounds [2]. The separation of
N-arylthio-, N-arylsulfinyl-, and N-arylsulfonyl-1,4-
benzoquinone monoimines is a difficult task due to their
similar solubility in many solvents and to close values
of their retention factors (Rf) hampering their chromato-
graphic isolation on SiO2. Therefore this method is
unsuitable for preparation compounds with i-Pr, t-Bu
groups and chlorine atoms in the positions 2 and 6 of the
quinoid ring (XVIa–XVIe, XVIIe, and XVIIIc–
XVIIIe). This method is most suitable for the synthesis
of unsubstituted, mono- and disubstituted in the quinoid
In the reaction carried out in ether or dioxane in the
presence of triethylamine the formed N-arylsulfinyl-4-
aminophenols were not isolated from the reaction mixture
and immediately were subjected to oxidation with silver
oxide or lead tetraacetate. Yields of the target products
were 50–60%.
This method of synthesis of N-arylsulfinyl-1,4-benzo-
quinone imines provides sufficiently pure reaction
products. But stringent requirements with respect to the
purity of initial compounds and quality of solvents, the
labor-consuming procedure of preparation of initial
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COMPARISON OF PREPARATION METHODS OF N-ARYLSULFINYL-1,4-BENZOQUINONE...
233
precipitate thus formed was recrystallized from the
glacial acetic acid.
arylsulfinyl chlorides, and also an additional oxidation
stage make this process less favorable that the oxidation
of N-arylthio-1,4-benzoquinone imines that provides
sufficiently pure reaction products in good yields except
for compounds XVIa–XVIe, XVIIe, and XVIIIc–
XVIIIe. In event of formation of difficultly removable
disulfides method a can be applied based on the reaction
between arenesulfenyl chlorides and p-benzoquinone
monooximes.
The characteristics of quinone imines IIIa–IIIe are
reported in [13], of quinone imine IVc, IVe, and VIe, in
[10], of quinone imines IVd, VIa–VId, in [2], of quinone
imines Ve and VIIe, in [1].
N-[(4-Methoxyphenyl)thio]-2-methyl-1,4-benzo-
quinone imine (IVa).Yield 23%, mp 114–115°C. 1H NMR
spectrum, δ, ppm, Z-isomer, 34%: 6.97–7.57 d.d (4H,
Ar, JO 8.7 Hz), 7.40–7.44 d.d (1H, H5, J3,5 2.4,
J5,6 9.9 Hz), 6.96 q [1H, H3 J(2-Me, H3) 1.8 Hz], 6.55 d
(1H, H6, J5,6 9.9 Hz), 3.84 s (3H, MeO), 2.01 d (3H,
2-Me, J 1.5 Hz); E-isomer, 66%: 6.97–7.57 d.d (4H, Ar,
JO 8.7 Hz), 7.31 q [1H, H3, J(2-Me, H3) 1.2 Hz], 7.01–
7.05 d.d (1H, H5, J3,5 2.7, J5,6 9.9 Hz), 6.47 d (1H, H6,
J5,6 10.2 Hz), 3.84 s (3H, MeO), 2.09 d (3H, 2-Me,
J 0.9 Hz). Found, %: N 5.02, 5.04; S 11.51, 11.57.
C14H13NO2S. Calculated, %: N 5.05; S 11.56.
The composition and structure of compounds obtained
1
were proved by elemental analysis, IR and H NMR
spectra. In the IR spectra of N-arylsulfinyl-1,4-benzo-
quinone imines a characteristic absorption band of S=O
group was observed in the range 1070–1110 cm–1, also
appeared absorption bands in the region 1580–1600
(C=N) and 1640–1670 cm–1 (C=O).
EXPERIMENTAL
N-[(4-Methylphenyl)thio]-2-methyl-1,4-benzo-
quinone imine (IVb). Yield 59%, mp 86–87°C. H NMR
1H NMR spectra were registered on a spectrometer
Varian VXR-300 at operating frequency 300 MHz in
CDCl3 solutions, internal reference TMS. IR spectra were
recorded on a spectrophotometer UR-20 from KBr
pellets. Analysis of compounds obtained was done by
TLS on Silufol UV-254 plates. Chloroform was used as
solvent, eluent benzene–hexane, 10:1, development
under UV irradiation.
1
spectrum, δ, ppm, Z-isomer, 36%: 7.24–7.53 d.d (4H,
Ar, JO 8.1 Hz), 7.40–7.44 d.d (1H, H5, J3,5 2.4,
J5,6 9.9 Hz), 6.99 q [1H, H3, J(2-Me, H3) 1.5 Hz], 6.55 d
(1H, H6, J5,6 9.9 Hz), 2.39 s (3H, Me), 2.02 d (3H, 2-Me,
J 1.2 Hz); E-isomer, 64%: 7.24–7.53 d.d (4H, Ar,
JO 8.1 Hz), 7.31 q [1H, H3, J(2-Me, H3) 1.2 Hz], 7.04–
7.08 d.d (1H, H5, J3,5 3.0, J 5,6 9.9 Hz), 6.47 d (1H, H6,
J5,6 9.6 Hz), 2.39 s (3H, Me), 2.09 d (3H, 2-Me,
J 1.2 Hz). Found, %: N 5.26, 5.40; S 12.23, 12.31.
C14H13NOS. Calculated, %: N 5.36; S 12.27.
Arenesulfenyl chlorides Ia–Id were obtained by
procedure [11], Ie as in [12]. N-Arylthio-1,4-benzo-
quinone imines IIIa–IIIe–VIa–VIe, and VIIIe were
synthesized by acylation of p-aminophenols XIa–XIg
with appropriate arenesulfenyl chlorides Ia–Ie in the
presence of triethylamine. In this process the formed
N-arylthio-1,4-aminophenols were spontaneously oxidiz-
ed by air oxygen giving the corresponding N-arylthio-
1,4-benzoquinone imines.
N-[(4-Methoxyphenyl)thio]-2,6-dimethyl-1,4-
benzoquinone imine (Va). Yield 34%, mp 85–86°C.
1H NMR spectrum, δ, ppm: 6.97–7.56 d.d (4H, Ar,
JO 8.4 Hz), 7.27 q (1H, H5), 6.89 q [1H, H3, J(2-Me, H3)
1.2 Hz], 3.84 s (3H, MeO), 2.08 s (3H, 2-Me), 2.01 s
(3H, 6-Me). Found, %: N 4.79, 4.84; S 10.91, 10.98.
C15H15NO2S. Calculated, %: N 4.81; S 11.00.
N-Arylthio-1,4-benzoquinone imines IIa–IIe –
VIIa–VIIe, VIIIe, and IXc–IXe). To a dispersion of
2 mmol of p-aminophenol XIa–XId and XIf in 20 ml of
anhydrous ethyl ether was added an equimolar quantity
of an appropriate arylsulfenyl chloride Ia–Ie and of
triethylamine. The separated precipitate of triethylamine
hydrochloride was filtered off, and the filterate was
evaporated in a vacuum of water jet pump. The residue
obtained was washed with methanol and glacial acetic
acid and recrystallized from the glacial acetic acid or
from hexane. In the case of compounds VIIa–VIIe and
IXc–IXe the precipitate obtained was oxidized with
2.5 mmol of iodosobenzene diacetate in acetic acid; the
N-[(4-Methylphenyl)thio]-2,6-dimethyl-1,4-
benzoquinone imine (Vb). Yield 30%, mp 111–112°C.
1H NMR spectrum, δ, ppm: 7.23–7.52 d.d (4H, Ar,
JO 8.1 Hz), 7.23 q (1H, H5), 6.93 q [1H, H3, J(2-Me, H3)
1.2 Hz], 2.38 s (3H, Me), 2.08 d [3H, 2-Me, J(2-Me, H3)
0.9 Hz], 2.01 d [3H, 6-Me, J(6-Me, H5) 0.9 Hz]. Found,
%: N 5.01, 5.07; S 11.54, 11.61. C15H15NOS. Calculated,
%: N 5.09; S 11.64.
N-(Phenylthio)-2,6-dimethyl-1,4-benzoquinone
imine (Vc). Yield 29%, mp 147–148°C. 1H NMR spec-
trum, δ, ppm: 7.31–7.63 m (5H, Ph), 7.26 q (1H, H5),
6.95 q (1H, H3), 2.09 s (3H, 2-Me), 2.03 s (3H, 6-Me).
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AVDEENKO et al.
234
δ, ppm: 7.71 d (1H, H5, J 2.4 Hz), 7.39–7.64 m (5H, Ph),
7.41 d (1H, H3, J 2.4 Hz). Found, %: N 4.51, 4.63; S 10.55,
10.67. C12H7Cl2NOS. Calculated, %: N 4.64; S 10.61.
Found, %: N 5.33, 5.40; S 12.20, 12.31. C14H13NOS.
Calculated, %: N 5.36; S 12.27.
N-[(4-Chlorophenyl)thio]-2,6-dimethyl-1,4-benzo-
quinone imine (Vd).Yield 21%, mp 137–138°C. 1H NMR
spectrum, δ, ppm: 7.38–7.56 d.d (4H, Ar, JO 8.7 Hz),
7.22 q [1H, H5, J(H5, 6-Me) 1.5 Hz], 6.93 q [1H, H3,
J(2-Me, H3) 1.5 Hz], 2.09 d [3H, 2-Me, J(2-Me, H3)
1.5 Hz], 2.03 d [3H, 6-Me, J(6-Me, H5) 1.2 Hz]. Found,
%: N 4.65, 4.77; S 10.71, 10.83. C14H12ClNOS.
Calculated, %: N 4.74; S 10.84.
N-[(4-Chlorophenyl)thio]-2,6-dichloro-1,4-benzo-
quinone imine (IXd). Yield 32%, mp 168°C. 1H NMR
spectrum, δ, ppm: 7.68 d (1H, H5, J 2.7 Hz), 7.44–
7.58 d.d (4H, Ar, JO 8.7 Hz), 7.41 d (1H, H3, J 2.7 Hz).
Found, %: N 4.11, 4.15; S 9.41, 9.52. C12H6Cl3NOS.
Calculated, %: N 4.16; S 9.53.
N-[(4-Nitrophenyl)thio]-2,6-dichloro-1,4-benzo-
quinone imine (IXe). Yield 30%, mp 262°C. 1H NMR
spectrum, δ, ppm: 7.79–8.35 d.d (4H, Ar, JO 9.0 Hz),
7.68 d (1H, H5, J 2.7 Hz), 7.48 d (1H, H3, J 2.4 Hz).
Found, %: N 8.01, 8.11; S 9.17, 9.26. C12H6Cl2N2O3S.
Calculated, %: N 8.07; S 9.24.
N-[(4-Methoxyphenyl)thio]-2,6-di-tert-butyl-1,4-
benzoquinone imine (VIIa). Yield 25%, mp 117–119°C.
1H NMR spectrum, δ, ppm: 6.97–7.58 d.d (4H, Ar,
JO 8.7 Hz), 7.22 d (1H, H5, J3,5 3.0 Hz), 6.86 d (1H, H3,
J3,5 2.7 Hz), 3.85 s (3H, MeO), 1.34 C (9H, 2-t-Bu),
1.28 s (9H, 6-t-Bu). Found, %: N 3.96, 3.99; S 8.85, 8.93.
C21H27NO2S. Calculated, %: N 3.92; S 8.96.
Arylsulfinyl chlorides Xa–Xe were prepared by
procedure [6].
N-Arylsulfinyl-1,4-benzoquinone imines XIIa–
XIIed–XIVa–XIVe, XVIa–XVIe, XVIIe, and XVIIIc–
XVIIIe. a. The preparation of quinone imines by
acylating with arenesulfenyl chlorides Ia–Ie the
corresponding 1,4-benzoquinone oximes IIa–IIg was
described in [1].
N-[(4-Methylphenyl)thio]-2,6-di-tert-butyl-1,4-
benzoquinone imine (VIIb). Yield 25%, mp 101–102°C.
1H NMR spectrum, δ, ppm: 7.24–7.54 d.d (4H, Ar,
JO 8.4 Hz), 7.21 d (1H, H5, J3,5 3.0 Hz), 6.89 d (1H, H3,
J3,5 2.7 Hz), 2.38 s (3H, Me), 1.34 C (9H, 2-t-Bu), 1.29 s
(9H, 6-t-Bu). Found, %: N 3.81, 3.95; S 8.87, 8.90.
C21H27NOS. Calculated, %: N 3.90; S 8.92.
b. The oxidation of N-arylthio-1,4-benzoquinone
imines with m-chloroperbenzoic acid was reported in [2].
N-(Phenylthio)-2,6-di-tert-butyl-1,4-benzoquinone
1
c. In 20 ml of ethyl ether 5 mmol of p-aminophenol
XIa–XIc, XIe–XIg was dispersed, and 5.5 mmol of
triethylamine was added. To this dispersion was added
at stirring 5.5 mmol of an appropriate sulfinyl chloride
Xa–Xe. The formed thick mass 10 min later was filtered
off, washed with water and a little methanol. On drying
the precipitate was dissolved in 30 ml of acetone, and at
stirring 5.5 mmol of silver oxide was added. After
30 min the reaction mixture was filtered through a silica
gel bed, the filtrate was evaporated, and the residue was
recrystallized from petroleum ether of bp 40–60°C.
imine (VIIc). Yield 30%, mp 103–105°C. H NMR
spectrum, δ, ppm: 7.31–7.65 m (5H, Ph), 7.21 d (1H,
H5, J3,5 2.7 Hz), 6.92 d (1H, H3, J3,5 2.7 Hz), 1.34 s (9H,
2-t-Bu), 1.29 s (9H, 6-t-Bu). Found, %: N 3.97, 4.09;
S 9.15, 9.32. C20H25NOS. Calculated, %: N 4.05; S 9.28.
N-[(4-Chlorophenyl)thio]-2,6-di-tert-butyl-1,4-
benzoquinone imine (VIId). Yield 22%, mp 112–113°C.
1H NMR spectrum, δ, ppm: 7.39–7.58 d.d (4H, Ar,
JO 8.7 Hz), 7.17 d (1H, H5, J3,5 2.7 Hz), 6.89 d (1H, H3,
J3,5 3.0 Hz), 1.34 s (9H, 2-t-Bu), 1.29 s (9H, 6-t-Bu).
Found, %: N 3.51, 3.67; S 8.32, 8.45. C20H24ClNOS.
Calculated, %: N 3.69; S 8.44.
N-arylsulfinyl-2,5-dimethyl-1,4-benzoquinone
imines XVa–XVe. a. To a solution of 5 mmol of 2,5-di-
methyl-4-aminophenol in 10 ml of dioxane was added at
stirring 5.5 mmol of triethylamine and then was charged
5.5 mmol of an appropriate arylsulfinyl chloride Xa–
Xe. The stirring was continued for 15 min, then at cooling
6 mmol of lead tetraacetate was added, and the separated
yellow precipitate was quickly filtered off, the filtrate
was evaporated, and the residue was recrystallized from
petroleum ether of bp 40–60°C.
N-[(4-Nitrophenyl)thio]-2,6-diisopropyl-1,4-
benzoquinone imine (VIIIe). Yield 25%, mp 144–
146°C. 1H NMR spectrum, δ, ppm: 7.79–8.31 d.d (4H,
Ar, JO 9.0 Hz), 7.11 d.d [1H, H5, J3,5 0.9, J(H5, 6-CH)
2.4 Hz], 6.92 d.d [1H, H3, J3,5 0.9, J(2-CH, H3) 2.7 Hz],
3.08–3.22 m (2H, 2,6-i-Pr), 1.19 d (6H, 2-i-Pr, J 6.9 Hz),
1.17 d (6H, 6-i-Pr, J 7.5 Hz). Found, %: N 7.65, 7.79;
S 8.73, 8.89. C18H20N2O3S. Calculated, %: N 7.73;
S 8.85.
The characteristics of quinone imines XIIId, XIVa,
XIVb, XIVd, XVa–XVd are described in [2], of quinone
imines XIVe and XVIe, in [1].
N-(Phenylthio)-2,6-dichloro-1,4-benzoquinone
imine (IXc). Yield 29%, mp 186°C. 1H NMR spectrum,
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COMPARISON OF PREPARATION METHODS OF N-ARYLSULFINYL-1,4-BENZOQUINONE...
235
N-[(4-Methoxyphenyl)sulfinyl]-1,4-benzoquinone
imine (XIIa). Yield 32% (a), 73% (b), 56% (c), mp 89–
MeO), 2.03 br.s (3H, 2-Me). Found, %: N 4.59, 4.72;
S 10.80, 10.94. C14H13NO3S. Calculated, %: N 4.77;
S 10.93.
1
90°C. H NMR spectrum, δ, ppm: 8.48–8.52 d.d (1H,
H5, J3,5 3.0, J5,6 9.9 Hz), 7.04–7.74 d.d (4H, Ar,
JO 9.0 Hz), 7.01–7.05 d.d (1H, H3, J3,5 2.1, J2,3 9.9 Hz),
6.57–6.61 d.d (2H, H2,6, J2,6 2.4, J2,3 9.3 Hz), 3.87 s (3H,
MeO). Found, %: N 4.89, 4.97; S 11.31, 11.50.
C13H11NO3S. Calculated, %: N 5.01; S 11.48.
N-[(4-Methylphenyl)sulfinyl]-2-methyl-1,4-
benzoquinone imine (XIIIb). Yield 34% (a), 70% (b),
53% (c), mp 68–69°C. 1H NMR spectrum, δ, ppm,
Z-isomer, 51%: 8.28 q (1H, H3), 7.33–7.69 d.d (4H, Ar,
JO 8.4 Hz), 6.95–6.98 d.d (1H, H5, J3,5 1.5, J5,6 9.9 Hz),
6.56 d (1H, H6, J5,6 9.9 Hz), 2.42 s (3H, Me), 2.07 br.s
(3H, 2-Me); E-isomer, 49%: 8.41–8.45 d.d (1H, H5,
J3,5 1.5, J5,6 9.6 Hz), 7.33–7.69 d.d (4H, Ar, JO 8.4 Hz),
6.83 q (1H, H3), 6.56 d (1H, H6, J5,6 9.9 Hz), 2.42 s (3H,
Me), 2.02 br.s (3H, 2-Me). Found, %: N 5.01, 5.09;
S 11.46, 11.57. C14H13NO2S. Calculated, %: N 5.05;
S 11.56.
N-[(4-Methylphenyl)sulfinyl]-1,4-benzoquinone
imine (XIIb). Yield 39% (a), 82% (b), 59% (c), mp 87–
1
88°C. H NMR spectrum, δ, ppm: 8.49–8.54 d.d (1H,
H5, J3,5 2.1, J5,6 9.9 Hz), 7.35–7.70 d.d (4H, Ar,
JO 8.4 Hz), 7.01–7.05 d.d (1H, H3, J3,5 2.8, J2,3 8.7 Hz),
6.56–6.60 d.d (2H, H2,6, J2,6 2.4, J2,3 9.6 Hz), 2.43 s (3H,
Me). Found, %: N 5.23, 5.34; S 12.11, 12.23.
C13H11NO2S. Calculated, %: N 5.32; S 12.18.
N-(Phenylsulfinyl)-2-methyl-1,4-benzoquinone
imine (XIIIc). Yield 45% (a), 66% (b), 51% (c),
mp 80°C. 1H NMR spectrum, δ, ppm, Z-isomer, 54 %:
8.30 q (1H, H3), 7.54–7.82 m (5H, Ph), 6.96–6.98 d.d
(1H, H5, J3,5 2.1, J5,6 9.9 Hz), 6.56 d (1H, H6,
J5,6 9.9 Hz), 2.08 br.s (3H, 2-Me); E-isomer, 46%: 8.42–
8.47 d.d (1H, H5, J3,5 2.1, J5,6 10.2 Hz), 7.54–7.82 m
(5H, Ph), 6.88 q (1H, H3), 6.56 d (1H, H6, J5,6 9.9 Hz),
2.03 br.s (3H, 2-Me). Found, %: N 5.25, 5.31; S 12.13,
12.21. C13H11NO2S. Calculated, %: N 5.32; S 12.18.
N-(Phenylsulfinyl)-1,4-benzoquinone imine (XIIc).
Yield 45% (a), 74% (b), 54% (c), mp 82–83°C. 1H NMR
spectrum, δ, ppm: 8.51–8.55 d.d (1H, H5, J3,5 3.0,
J5,6 9.6 Hz), 7.55–7.83 m (5H, Ph), 7.02–7.06 d.d (1H,
H3, J3,5 2.4, J2,3 9.6 Hz), 6.57–6.61 d.d (2H, H2,6
,
J2,6 2.7, J2,3 10.2 Hz). Found, %: N 5.59, 5.65; S 12.81,
12.91. C12H9NO2S. Calculated, %: N 5.62; S 12.86.
N-[(4-Chlorophenyl)sulfinyl]-1,4-benzoquinone
imine (XIId). Yield 42% (a), 84% (b), 55% (c), mp 117–
119°C. 1H NMR spectrum, δ, ppm: 8.46–8.51 d.d (1H,
H5, J3,5 2.7, J5,6 9.9 Hz), 7.52–7.77 d.d (4H, Ar, JO 9.0 Hz),
7.01–7.05 d.d (1H, H3, J3,5 2.7, J2,3 9.9 Hz), 6.58–
6.61 d.d (2H, H2,6, J2,3 10.5 Hz). Found, %: N 4.93, 4.97;
S 11.21, 11.33. C12H8ClNO2S. Calculated, %: N 4.98;
S 11.30.
N-[(4-Nitrophenyl)sulfinyl]-2-methyl-1,4-
benzoquinone imine (XIIIe). Yield 31% (a), 65% (b),
1
52% (c), mp 115–116°C. H NMR spectrum, δ, ppm,
Z-isomer, 52%: 8.25 q (1H, H3), 8.01–8.42 d.d (4H, Ar,
JO 9.0 Hz), 6.95–6.99 d.d (1H, H5, J3,5 1.5, J5,6 9.6 Hz),
6.59d (1H, H6, J5,6 9.0 Hz), 2.09 br.s (3H, 2-Me); E-iso-
mer, 48%: 8.42–8.46 d.d (1H, H5, J3,5 1.5, J5,6 9.6 Hz),
8.01–8.42 d.d (4H, Ar, JO 9.0 Hz), 6.88 q (1H, H3),
6.59 d (1H, H6, J5,6 9.0 Hz), 2.05 br.s (3H, 2-Me). Found,
%: N 9.01, 9.13; S 10.29, 10.37. C13H10N2O4S. Cal-
culated, %: N 9.09; S 10.40.
N-[(4-Nitrophenyl)sulfinyl]-1,4-benzoquinone
imine (XIIe). Yield 30% (a), 71% (b), 59% (c), mp 109–
1
110°C. H NMR spectrum, δ, ppm: 8.45–8.49 d.d (1H,
H5, J3,5 2.7, J5,6 9.9 Hz), 8.02–8.43 d.d (4H, Ar,
JO 8.7 Hz), 7.02–7.06 d.d (1H, H3, J3,5 2.7, J2,3 9.9 Hz),
6.59–6.64 d.d (2H, H2,6, J2,6 2.4, J2,3 9.9 Hz). Found, %:
N 9.46, 9.55; S 10.76, 10.89. C12H8N2O4S. Calculated,
%: N 9.52; S 10.90.
N-(Phenylsulfinyl)-2,6-dimethyl-1,4-benzoquinone
imine (XIVc). Yield 70% (a), 67% (b), 50% (c), mp 50–
52°C. 1H NMR spectrum, δ, ppm: 8.21 br.s (1H, H5),
7.53–7.82 m (5H, Ph), 6.82 br.s (1H, H3), 2.08 br.s (3H,
2-Me), 2.02 br.s (3H, 6-Me). Found, %: N 4.93, 4.99;
S 11.44, 11.59. C14H13NO2S. Calculated, %: N 5.05;
S 11.56.
N-[(4-Methoxyphenyl)sulfinyl]-2-methyl-1,4-
benzoquinone imine (XIIIa). Yield 30% (a), 82% (b),
60% (c), mp 99–100°C. 1H NMR spectrum, δ, ppm,
Z-isomer, 48%: 8.25 q (1H, H3), 7.03–7.74 d.d (4H, Ar,
JO 9.0 Hz), 6.95–6.99 d.d (1H, H5, J3,5 2.7, J5,6 9.9 Hz),
6.57 d (1H, H6, J5,6 9.9 Hz), 3.86 s (3H, MeO), 2.08 br.s
(3H, 2-Me); E-isomer, 52%: 8.38–8.43 d.d (1H, H5,
J3,5 2.4, J5,6 10.2 Hz), 7.03–7.74 d.d (4H, Ar, JO 9.0 Hz),
6.88 q (1H, H3), 6.57 d (1H, H6, J5,6 9.9 Hz), 3.86 s (3H,
N-[(4-Nitrophenyl)sulfinyl]-2,5-dimethyl-1,4-
benzoquinone imine (XVe). Yield 42% (a), 85% (b),
1
53% (c), mp 153–155°C. H NMR spectrum, δ, ppm:
8.20 q [1H, H3, J(2-Me, H3) 1.5 Hz], 8.02–8.43 d.d (4H,
Ar, JO 9.0 Hz), 6.47 q [1H, H6, J(Me5, H6) 1.5 Hz],
2.12 d [3H, 2-Me, J(2-Me, H3) 1.5 Hz], 2.07 d [3H, Me5,
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AVDEENKO et al.
236
J(Me5, H6) 1.5 Hz]. Found, %: N 8.53, 8.70; S 9.87, 9.99.
C14H12N2O4S. Calculated, %: N 8.69; S 9.95.
N-[(4-Chlorophenyl)sulfinyl]-2,6-dichloro-1,4-
benzoquinone imine (XVIIId). Yield 30% (a), 65% (b),
1
50% (c), mp 146–148°C. H NMR spectrum, δ, ppm:
N-[(4-Methoxyphenyl)sulfinyl]-2,6-di-tert-butyl-
1,4-benzoquinone imine (XVIa). Yield 40% (a), 67%
(b), 50% (c), mp 66–69°C. 1H NMR spectrum, δ, ppm:
8.08 d (1H, H5, J3,5 1.2 Hz), 7.03–7.76 d.d (4H, Ar,
JO 8.7 Hz), 6.77 d (1H, H3, J3,5 1.2 Hz), 3.86 s (3H, MeO),
1.30 br.s (9H, 2-t-Bu), 1.26 br.s (9H, 6-t-Bu). Found, %:
N 3.64, 3.71; S 8.55, 8.61. C21H27NO3S. Calculated, %:
N 3.75; S 8.58.
8.80 d (1H, H5, J3,5 1.8 Hz), 7.53–7.76 d.d (4H, Ar,
JO 8.4 Hz), 7.26 d (1H, H3, J3,5 2.4 Hz). Found, %: N
4.12, 4.24; S 9.46, 9.53. C12H6Cl3NO2S. Calculated, %:
N 4.19; S 9.58.
N-[(4-Nitrophenyl)sulfinyl]-2,6-dichloro-1,4-
benzoquinone imine (XVIIIe). Yield 33% (a), 67% (b),
1
56% (c), mp 155–158°C. H NMR spectrum, δ, ppm:
8.77 d (1H, H5, J3,5 2.1 Hz), 8.01–8.44 d.d (4H, Ar,
JO 8.7 Hz), 7.28 d (1H, H3, J3,5 2.4 Hz). Found, %: N 7.63,
7.69; S 8.71, 8.85. C12H6Cl2N2O4S. Calculated, %:
N 7.71; S 8.83.
N-[(4-Methylphenyl)sulfinyl]-2,6-di-tert-butyl-1,4-
benzoquinone imine (XVIb). Yield 32% (a), 69% (b),
1
58% (c), mp 60°C. H NMR spectrum, δ, ppm: 8.12 d
(1H, H5, J3,5 1.8 Hz), 7.34–7.72 d.d (4H, Ar, JO 8.4 Hz),
6.76 d (1H, H3, J3,5 1.8 Hz), 2.42 s (3H, Me), 1.30 br.s
(9H, 2-t-Bu), 1.25 br.s (9H, 6-t-Bu). Found, %: N 3.65,
3.74; S 8.47, 8.61. C21H27NO2S. Calculated, %: N 3.73;
S 8.54.
REFERENCES
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Konovalova S.A., and Yusina A.L., Zh. Org. Khim. 2004,
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lova A.A., and Vakulenko A.V., Arkivoc., 2005, vol. 8,
p. 57.
N-(Phenylsulfinyl)-2,6-di-tert-butyl-1,4-
benzoquinone imine (XVIc). Yield 44% (1), 66% (b),
1
58% (c), mp 100–102°C. H NMR spectrum, δ, ppm:
8.14 br.s (1H, H5), 7.54–7.85 m (5H, Ph), 6.76 br.s (1H,
H3), 1.31 br.s (9H, 2-t-Bu), 1.27 br.s (9H, 6-t-Bu). Found,
%: N 3.73, 3.85; S 8.71, 8.82. C20H25NO2S. Calculated,
%: N 3.87; S 8.87.
3. Oae S., Shinhama K., Fujimori K., and Yong Hae Kim,
Bull. Chem. Soc. Jpn. 1980, vol. 53, p. 775.
4. Adams R. and Reifschneider W., Bull. Soc. Chim. 1958,
vol. 1, p. 23; Burmistrov S.I. and Titov E.A., Zh. Obshch.
Khim. 1952, vol. 22, p. 999; Titov E.A. and Avdeen-
ko A.P., Zh. Org. Khim. 1972, vol. 8, p. 616.
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vol. 57, p. 2172.
6. Levchenko E.S., Derkach N.Ya., and Kirsanov A.V., Zh.
Obshch. Khim. 1961, vol. 31, p. 1971; Karade N.N.,
Kate S.S., andAdude R.N. Synlett. 2001, vol. 10, p. 1573.
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Vopr. khim. i khim. tekhnol. 2005, vol. 3, p. 37.
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vol. 24, p. 1154.
N-[(4-Chlorophenyl)sulfinyl]-2,6-di-tert-butyl-1,4-
benzoquinone imine (XVId). Yield 45% (a), 71% (b),
54% (c), mp 75–78°C. 1H NMR spectrum, δ, ppm: 7.53–
7.97 d.d (4H, Ar, JO 8.4 Hz), 7.88 br.s (1H, H5), 6.67 br.s
(1H, H3), 1.33 br.s (9H, 2-t-Bu), 1.26 br.s (9H, 6-t-Bu).
Found, %: N 3.41, 3.43; S 8.02, 8.13. C20H24ClNO2S.
Calculated, %: N 3.54; S 8.10.
N-[(4-Nitrophenyl)sulfinyl]-2,6-diisopropyl-1,4-
benzoquinone imine (XVIIe). Yield 34% (a), 65% (b),
51% (c), mp 84–88°C. 1H NMR spectrum, δ, ppm: 8.03–
8.42 d.d (4H, Ar, JO 8.7 Hz), 8.09 br.s (1H, H5),
6.72 br.s. (1H, H3), 3.05–3.22 m (2H, 2,6-CH i-Pr),
1.19 d (6H, 2-i-Pr, J 7.5 Hz), 1.16 d (6H, 6-i-
Pr, J 7.2 Hz). Found, %: N 7.32, 7.44; S 8.39, 8.52.
C18H20N2O4S. Calculated, %: N 7.40; S 8.47.
9. Dubina V.L. and Burmistrov K.S., Zh. Org. Khim. 1977,
vol. 13, p. 378.
N-(Phenylsulfinyl)-2,6-dichloro-1,4-benzoquinone
imine (XVIIIc). Yield 40% (a), 69% (b), 53% (c), mp 77–
10. AvdeenkoA.P., Konovalova S.A., and SantalovaA.A., Zh.
Org. Khim. 2007, vol. 43, p. 1479.
11. Almast L. and HantzA., Chem. Ber. 1961, vol. 94, p. 728.
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13. Pirozhenko V.V., Burmistrov K.S., Belov V.V., and
Nichvoloda V.I., Ukr. Khim. Zh., 1992, vol. 58, p. 68.
1
80°C. H NMR spectrum, δ, ppm: 8.86 d (1H, H5,
J3,5 2.1 Hz), 7.56–7.82 m (5H, Ph), 7.28 d (1H, H3,
J3,5 2.4 Hz). Found, %: N 4.31, 4.43; S 9.91, 10.03.
C12H7Cl2NO2S. Calculated, %: N 4.40; S 10.08.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008