Halogenation of N-substituted p-quinone monoimines and p-quinonemonooxime ethers: XII. halogenation of n-aroyl-2(3)-methyl-1,4-benzoquinone monoimines and their reduced forms

Article abstract of DOI:10.1134/S1070428010110035

A strong acceptor substituent at the nitrogen atom of the N-substituted p-quinone monoimine decreases the stability of the halogen-containing cyclohexene structures formed at the addition of a halogen molecule to the C=C bond of the quinoid ring. As a res

Full text of DOI:10.1134/S1070428010110035

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1629−1638. © Pleiades Publishing, Ltd., 2010.
Original Russian Text ©A.P. Avdeenko, S.A. Konovalova, O.N. Ludchenko, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 11, pp. 1624−1633.
Halogenation of N-substituted p-Quinone Monoimines
and p-Quinonemonooxime Ethers: XII.*
Halogenation of N-Aroyl-2(3)-methyl-1,4-benzoquinone
Monoimines and Their Reduced Forms
A. P. Avdeenko, S. A. Konovalova, and O. N. Ludchenko
Donbass State Mashine-Building Academy, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
Received March 1, 2010
Abstract—Astrong acceptor substituent at the nitrogen atom of the N-substituted p-quinone monoimine decreases
the stability of the halogen-containing cyclohexene structures formed at the addition of a halogen molecule to the
C=C bond of the quinoid ring.As a result of the bromination of N-benzoyl-2-methyl-1,4-benzoquinone monoimine
alongside the usual products of addition and substitution the 5-benzoyloxy-2,3,6-tribromo-6-methylcyclohex-2-
ene-1,4-dione was isolated.
DOI: 10.1134/S1070428010110035
This study is a continuation of the research on the
halogenation processes of N-substituted 1,4-benzoqui-
none monoimines. We formerly investigated in detail
the halogenation of various N-arylsulfonyl-1,4-benzo-
quinone monoimines and their reduced forms [2–4],
4-amino-N-aroylphenol without substituents in the ring
of the aminophenol [5], and N-aroyl-1,4-benzoquinone
monoimines with two alkyl substituents in the ring [6,
7]. The N-aroyl-1,4-benzoquinone monoimines unsubsti-
tuted in the quinoid ring were not previously examined
due to their instability [5, 8].
fast Z,E-isomerization occurs, and notwithstanding the
existence of two isomeric forms the 1H NMR spectrum
contains a single set of signals, namely, the degenerate
Z,E-isomerization is observed. It was earlier established
that the presence of the Z,E-isomerization significantly
affected the halogenation course of the N-arylsulfonyl-
1,4-benzoquinone monoimines [3].
The difference in the chemical shifts of protons H5 and
H6 (H2 and H3) of the quinoid ring is not so pronounced
in the 1H NMR spectra of compounds I, II as in the case
of N-arylsulfonyl derivatives. This is due to the fact that
the chemical shifts of the protons of the quinoid ring of
N-aroyl derivatives A because of the fast Z,E-isomeri-
zation depend mainly on the position of this proton in
the ring and on the character of the substituents in the
neighboring positions. In N-arylsulfonyl derivatives B
the chemical shifts of the protons in the quinoid ring are
strongly affected by the position of the substituent at the
nitrogen atom (cis- or trans-): the signal of the proton
in the position 5 of the quinoid ring is shifted downfield
and appears in the region 7.92–8.18 [3], of the proton H3,
in the region 6.81–6.93 ppm. In aroyl derivatives A the
signal of the atom H5 of quinone imines Ia, Ib is shifted
upfield compared with the sulfonyl derivatives and ap-
pears in the region 7.02–7.08, and that of the atom H3,
In this study N-aroyl-2(3)-methyl-1,4-benzoquinone
monoimines I, II and 4-amino-N-aroyl-2(3)-methyl-phe-
nols III, IV were chosen as the objects of the investigation.
In contrast to the corresponding N-arylsulfonyl-2-methyl-
1,4-benzoquinone monoimines [3] the 1H NMR spectra
of N-aroyl-2-methyl-1,4-benzoquinone monoimines
Ia, Ib contain a single set of signals. It was established
formerly that the N-aroyl-1,4-benzoquinone monoimines
had a lower barrier to the Z,E-isomerization [9] (ΔG≠
298K
44–46 kJ mol–1), than N-arylsulfonyl derivatives [10]
(ΔG≠298Q 65–80 kJ mol–1). Therefore in the solutions of
compounds Ia, Ib already at the room temperature the
* For Communication XI, see [1].
1629

AVDEENKO et al.
1630
at 6.85–6.87 ppm.
after the oxidation of 4-amino-N-aroyl-2-methylphenols
IIIa, IIIc and 4-amino-N-benzoyl-3-methylphenol (IVa)
for the reaction products were uncrystallizable oily sub-
stances. We succeeded to isolate in the crystalline state
only bromo- and nitrobenzoyl derivatives Ia, Ib and N-
aroyl-3-methyl-1,4-benzoquinone monoimines IIb, IIc.
O
S
O
O
5
6
5
6
Ar
Ar
C
N
O
N
O
2
Me2
3
3
Me
The equimolar chlorination of quinone monoimines
Ia, Ib in acetic acid afforded 6-chlorophenols Va, Vb,
and in DMF, a mixture of 5,6- and 3,6-dichloro-1,4-
benzoquinone monoimines IXa, IXb and Xa, Xb with
the prevalence of the latter (Scheme 1). At the increased
excess of chlorine to 1:2 uncrystallizable oily intractable
mixtures of compounds were obtained.
A
B
The special feature of p-quinone monoimines consists
in the dependence of their redox potential on the nature
of the substituent at the nitrogen atom [11]. The presence
of a strong acceptor substituent at the nitrogen atom in
the N-aroyl-1,4-benzoquinone monoimines significaly
increases their redox potential, and this should inevitably
affect the halogenation, for the redox processes play there
a significant part.
The structures of quinone monoimines IXa, IXb and
Xa, Xb were identified from the 1H NMR spectra. The
quartet signal of atom H3 of quinone monoimines IXa,
IXb appeared in the region 6.82–6.86 ppm. The location
of the signal confirmed the whereabouts of the proton in
the ortho-position to the C=N fragment of the quinoid
ring, its form was due to the coupling with the protons
of the CH3 group whose doublet was observed at 2.06–
2.09 ppm. In the 1H NMR spectra of quinone monoimines
Xa, Xb the singlet of the atom H5 located in the ortho-
position to the imine carbon atom appeared in the region
7.16–7.21 ppm and was shifted downfield compared to
the signal of the proton H3 of quinone monoimines IXa,
IXb. The protons of CH3 group give rise to a singlet at
2.33–2.35 ppm confirming the presence of the chlorine
atom in the position 3 of the quinoid ring.
The goal of this study is the investigation of the ha-
logenation of the N-aroyl-2(3)-methyl-1,4-benzoquinone
monoimines and the comparison of the results obtained
with the previously examined halogenation processes
of the corresponding N-arylsulfonyl-1,4-benzoquinone
monoimines.
The halogenation of N-aroyl-2(3)-methyl-1,4-benzo-
quinone monoimines Ia, Ib and IIa, IIb, 4-amino-N-
aroyl-2(3)-methylphenols IIIa–IIIc and IVa–IVc was
carried out using gaseous chlorine and molecular bromine
in CHCl3, AcOH, DMF, a mixture DMF–AcOH, 1:5, at
various ratios initial substrate–halogen.
N-Aroyl-2(3)-methyl-1,4-benzoquinone monoimines
were obtained by the oxidation of the corresponding
aminophenols with lead tetraacetate in acetic acid, but
we failed to isolate the respective quinone monoimines
The equimolar bromination of quinone monoimines
Ia, Ib in CHCl3, DMF, a mixture DMF–AcOH, 1 : 5,
resulted only in 6-bromophenols VIa, VIb (Scheme 1).
Scheme 1.
Me
O
Me
OH
O
O
[O]
X
C N
X
C NH
Pb(AcO)4
CH3
O
Hlg
Hlg
O
C
VIIa, VIIb, VIIIa, VIIIb
Hlg2
Va, Vb, VIa, VIb
X
N
Me
O
Cl
Me
O
O
Ia, Ib
+
X
C N
N
O
C
X
Cl
Cl
IXa, IXb
X = Br (a), NO2 (b); Hlg = Cl (V, VII), Br (VI, VIII).
Cl
Xa, Vb
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES...: XII.
1631
The equimolar chlorination of aminophenols IIIa,
IIIb in the mixture DMF–AcOH, 1 : 5, led to the for-
mation of substituted 5,6- and 3,6-dichlorophenols XIa,
XIb and XIVa, XIVb with the prevalence of the former.
At increasing the ratio initial substrate–chlorine
to 1 : 3 in CHCl3, AcOH, the mixture DMF–AcOH
we obtained stable 4-aroylimino-6-methyl-2,3,5,6-
tetrachloro-cyclohex-2-en-1-ones XVa, XVb. At the
chlorination of aminophenols IIIb, IIIc in DMF with
the triple excess of chlorine 3,5,6-trichloro deriva-
tives XVIb, XVIc were isolated originating from the
dehydrochlorination of 4-aroylimino-6-methyl-2,3,5,6-
tetrachlorocyclohex-2-en-1-ones XV. By increasing the
ratio initial substrate–chlorine to 1 : 5 in DMF
stable 6-methyl-4-(4-methyl-benzoyl)imino-2,3,5,5,6-
pentachlorocyclohex-2-en-1-one (XVII) was obtained.
At increasing the ratio initial compound–bromine from
1 : 2 to 1 : 5 only oily substances were obtained which
we failed to identify.
The structure of compounds Va, Vb, VIa, VIb was
1
established from the H NMR spectra of N-aroyl-2-
methyl-6-bromo(chloro)-1,4-benzoquinone monoimines
VIIa, VIIb and VIIIa, VIIIb obtained by the oxidation
of aminophenols Va, Vb, VIa, VIb with lead tetraacetate
in acetic acid.
In the 1H NMR spectra of quinone monoimines VIIa,
VIIb and VIIIa, VIIIb the quartet signal of the atom H3
was observed at 6.89–6.92, and the doublet of the atom
H5, in the region 7.25–7.55 ppm. The doublet of the
protons of the CH3 group appeared at 2.11–2.14 ppm in
good agreement with the assumed structure.
The chlorination of 2-methylphenols IIIa–IIIc in
CHCl3,AcOH, DMF at the ratio initial substrate–chlorine
1:1 resulted in 2-methyl-5,6-dichlorophenols XIa–XIc
(Scheme 2).
The structure of compounds XVa, XVb, XVIb, XVIc,
XVII was proved by the data of 1H and 13C NMR spectra.
The singlet of the atom H5 of the structures XVa, XVb
Scheme 2.
Me
OH
Me
O
O
C
[O]
HN
C
X
O
N
X
Hlg
IXb–IXd, XIIIa, XIIIc
Hlg
XIb–IXd, XIIIa, XIIc
Hlg
Hlg
Cl
O
Me
[O]
X
C
NH
OH
Xb, Xc
Br2
Cl
XIVa, XIVb
Me
OH
H Cl
Cl
O
C
O
C
O
C
Hlg2
Me
O
X
HN
H Br
O
N
X
Me
O
Cl
XVa, XVb
Cl Me
Cl
O
IIIa–IIIc
Br
XVIII
Br
O
X
O
C
N
Cl
Cl
XVIa, XVIb
Cl Cl
Me
O
O
C
Cl
N
Me
Cl
Cl
XVII
III, XI–XVI, X = H (a), NO2 (b), Me (c); IX, X = NO2 (b), Me (c), H (d); X, X = NO2 (b), H (c); Hlg = Cl (IX, XI), Br
(XII, XIII).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

AVDEENKO et al.
1632
appears in the region 5.01–5.03 ppm characteristic of the
protons attached to the sp3-hybridized carbon atom in the
ortho-position to the C=N fragment, the proton signal of
the CH3 group is observed as a singlet at 1.90–1.93 ppm.
In the case of quinone monoimines XVIb, XVIc the sin-
glet of the methyl protons is shifted downfield compared
to the methyl signal of the protons of XVa, XVb structure
and is observed at 2.22–2.27 ppm. In the spectrum of
compound XVII the methyl singlet is located at 2.18 ppm.
The 13C NMR spectra of compounds XVa, XVII con-
tain characteristic upfield signals of two sp3-hybridized
carbon atoms: 64.81, 57.88 in the spectrum of com-
pound XVa (from fragments CClCH3, CHCl) and 88.77,
72.27 ppm for compound XVII (CClCl and CClCH3). In
the 13C NMR spectrum of compound XVIc the signals of
sp3- hybridized carbon atoms are absent, and the observed
signals are totally consistent with the assumed structure.
4-amino-N-arylsulfonyl-2-methylphenols no compounds
of similar structure were isolated [3], but they were ob-
tained at the bromination of N-aroyl-2,6(2,5)-dimethyl-
1,4-benzoquinone monoimines [7].
The structure of compound XVIII was proved by the
1
data of H and 13C NMR spectra. The characteruistic
feature of this compound is the presence in the 1H NMR
spectrum of a signal from the H5 proton linked to the sp3-
hybridized carbon atom in the region 6.20, and the singlet
of the methyl protons at 2.01 ppm [7]. In the 13C NMR
spectrum of compound XVIII two characteristic peaks
of the carbonyl atoms C1 and C4 appeared at 181.46 and
180.33 ppm, and two signals of sp3-hybridized carbon
atoms were observed in the strong field (77.18 and
56.65 ppm).
The analysis of the experimental data of this study and
the former investigations [5–7] shows that the formation
of aminophenols XI, XII occurs as a result of the oxida-
tion of aminophenols III with a halogen molecule into
quinone monoimines I which add the molecule Hlg2 to the
free bond C=C of the quinoid ring giving 4-aroylimino-
5,6-dihalo-2-methylcyclohex-2-en-1-ones. We failed
to isolate the latter for due to the fast in the NMR scale
Z,E-isomerization they were very unstable and suffered
a prototropic rearrangement to provide aminophenols XI,
XII. Aminophenols XI, XII may also form as a result of
the electrophilic substitution of hydrogen atoms by halo-
gen in the molecules of aminophenols III.Aminophenols
XIV result from the electrophilic substitution of hydrogen
atoms by chlorine in the ring of aminophenols III.
The bromination of aminophenols IIIa, IIIc in CHCl3,
AcOH, the mixture DMF–AcOH furnished 4-amino-
N-aroyl-5,6-dibromo-2-methylphenols XIIa, XIIc
(Scheme 2). We failed to obtain products of deeper bro-
mination. It may be caused by the higher redox potential
of aroyl derivatives and impossible for bromine to oxidize
the obtained aminophenols XIIa, XIIc unlike the previ-
ously observed behavior of arylsulfonyl derivatives [3].
In order to identify aminophenols XIa–XIc, XIIa,
XIIc they were oxidized with lead tetraacetate in
acetic acid into the corresponding 1,4-benzoquinone
monoimines IXb–IXd, XIIIa, XIIIc since the 1H NMR
spectra of quinone monoimines were more informative.
The mixture of compounds XIa, XIb and XIVa, XIVb
also was analyzed after oxidation which yielded a mixture
of quinone monoimines IXb, IXd and 3,6-dichloro-1,4-
benzoquinone monoimines Xb, Xc.
The maximally chlorinated compound XVII is likely
to form through a sequence of transformations: (1) The
oxidation of aminophenol III to quinone monoimine I
with a halogen molecule; (2) addition of the molecule
Cl2 to the free bond C=C of the quinoid ring of quinone
monoimine I with the formation of the unstable cyclohex-
ene structure which in the course of the reaction suffers
the prototropic rearrangement into aminophenol XI; (3)
aminophenol XI undergoes the oxidation and adds the
molecule Cl2 to the methyl-substituted C=C bond giving
compound XV; (4) tetrachlorocyclohexene structure XV
suffers the dehydrochlorination to form trichloroquinone
monoimine XVI that adds the molecule Cl2 to the methyl-
substituted C=C bond affording the compound of the
maximum degree of chlorination the pentachlorocyclo-
hexene structure XVII.
1
In the H NMR spectrum of quinone monoimines
IXb–IXd, XIIIa, XIIIc the quartet of the proton H3 ap-
peared in the region 6.82–6.88, and the doublet of the
methyl protons, at 2.04–2.05 ppm, unambiguously con-
firming the structure of these compounds. In the spectra
of quinone monoimines Xb, Xc the singlet of the atom
H5 is present in the region 7.16–7.21 ppm, and the singlet
of the methyl protons, at 2.33–2.35 ppm, in agreement
with the assumed structure.
The bromination of aminophenol XIIa and quinone
monoimine XIIIa in DMF and its mixture with ACOH
at the ratio substrate–bromine 1 : 10 provided 5-benzo-
yloxy-2,3,6-tribromo-6-methylcyclohex-2-en-1,4-dione
(XVIII). Formerly at the bromination of the analogous
The chlorination of quinone monoimines IIa, IIb and
aminophenols IVa–IVc in various solvents at different
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES...: XII.
1633
Scheme 3.
Me
O
X
C NH
OH
Hlg
XIXc, XXa
Me
C NH
Hlg
OH
Hlg
XXIa–XXIc, XXIIa–XXIIc
O
X
Me
NH
Cl
Cl
O
C
X
OH
[O]
Me
Me
O
O
C
Hlg2
Hlg2
Cl
X
C NH
X
OH
N
O
XXIIIb, XXIIc
Hlg
Me
O
IVa–IVc
IIb, IIc
O
X
NC
Hlg
XXIVa–XXIVc, XXVa–XXVc
Me
Cl
O
C
X
O
N
Cl
Cl
XXVIa–XXIVc
Cl Cl
Me
Cl
O
O
C
X
N
Cl
XXVIIa–XXVIIc
Cl
X = H (a), Me (b), Cl (c), Hlg = Cl (XIX, XXI, XXIV), Br (XX, XXII, XXV).
ratios initial substance–chlorine led to the formation of
compounds shown in Scheme 3. In a single case, at the
chlorination of 3-methyl-N-(4-chlorobenzoyl)-1,4-benzo-
quinone monoimine (IIc) at the ratio initial substance–
chlorine 1 : 1 in CHCl3 or the mixture DMF–AcOH,
1 : 5 we obtained 6-chloro derivative XIXc in a mixture
with 2,6-dichlorocompound XXIc (Scheme 3).
aminophenols XXIa–XXIc with lead tetraacetate in
acetic acid leads to the formation of N-aroyl-3-methyl-
2,6-dichloro-1,4-benzoquinone monoimines XXIVa–
XXIVb which were also obtained by the chlorination of
quinone monoimines IIb, IIc in DMF at the ratio initial
substance–chlorine 1 : 1.At the excess of the chlorinating
agent (1 : 3.5) the chlorination of the quinone monoimines
IIb, IIc and aminophenols IVa–IVc in CHCl3, AcOH,
the mixture DMF–AcOH, 1 : 5, resulted in N-aroyl-3-
methyl-2,5,6-trichloro-1,4-benzoquinone monoimines
XXVIa–XXVIc. The products of the highest chlorination
degree XXVIIa–XXVIIc were obtained at the chlorina-
tion of quinone monoimines IIb, IIc and aminophenols
IVa–IVc only in DMF at the highest ratio initial sub-
Individual aminophenols XXIa–XXIc were obtained
by the equimolar chlorination of quinone monoimines
IIa, IIb in AcOH and aminophenols IVa–IVc in CHCl3,
AcOH, DMF, the mixture DMF–AcOH. The chlorination
of quinone monoimines IIb, IIc in CHCl3 gave a mixture
of 2,6-dichloro- (XXIb, XXIc) and 2,5,6-trichlorophe-
nols (XXIIIb, XXIIIc) (Scheme 3). The oxidation of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

AVDEENKO et al.
1634
stance–chlorine (1 : 6.5).
carbon atom leading to a high reactivity of the cyclo-
hexene compounds and to the fast dehydrohalogenation
of the latter. As a result of the dehydrohalogenation or
a prototropic rearrangement the cyclohexene compounds
convert into the corresponding quinone monoimines or
aminophenols. On the other hand, by the chlorination of
quinone monoimines II and aminophenols III, IV we
obtained the product of the maximum degree of haloge-
nation, compounds XVII and XXVII that we had failed
to prepare from the corresponding N-arylsulfonyl deriva-
tives of p-quinone monoimines. This can be ascribed to
the stronger electron-acceptor properties of the aroyl
group compared to theArSO2 group and consequently to
the lower stability of the cyclohexene structures resulting
in the readily occurring processes of dehydrohalogena-
tion and further to the formation of quinone imines of the
maximum degree of halogenation.
The structure of compounds XXVIa–XXVIc, XXVI-
Ia–XXVIIc was proved by the 1H and 13C NMR spectra.
In the spectra of quinone monoimines XXVIIa–XXVIIc
the proton signal from the methyl group is observed at
2.29–2.30 ppm upfield from the signal of the methyl
protons of compounds XXVIa–XXVIc. In the 13C NMR
spectrum of compound XXVIIb the characteristic sig-
nals of two sp3-hybridized carbon atoms appear at 88.40
(CClCl) and 74.51 ppm (CClCH3).
The bromination of quinone monoimines IIa, IIb and
aminophenols IVa–IVc at the ratio initial substrate–bro-
mine from 1 : 3 to 1 : 5 in CHCl3, AcOH, the mixture
DMF–AcOH, 1 : 5, resulted in the formation of 2,6-di-
bromophenols XXIIa–XXIIc. The oxidation of the latter
and also the bromination of quinone monoimines IIa,
IIb in DMF at the ratio initial substrate–bromine 1 : 1
led to the formation of 2,6-dibromo-1,4-benzoquinone
monoimines XXVa–XXVc. The bromination of amino-
phenol IVa inAcOH, DMF at the same ratio initial sub-
strate–bromine yielded 6-bromophenol XXa (Scheme 3).
EXPERIMENTAL
IR spectra of compounds synthesized were recorded
on a spectrophotometer UR-20 from pellets with KBr. 1H
and 13C NMR spectra were registered on a spectrometer
Varian VXR-300 (300 and 75.4 MHz) from solutions in
CDCl3, internal reference TMS.
1
In the H NMR spectra of aminophenols XIX, XX
the singlet of the atom H2 is observed at 6.85–6.87, the
singlet of the atom H5, in the region 7.28–7.41 ppm, and
the singlet of the methyl protons, at 2.13 ppm, confirming
the structure of these compounds.
The reaction mixtures were analyzed by TLC on Si-
lufol UV-254 plates, eluent benzene–hexane, 10 : 1, ben-
zene–ethyl acetate, 10:1, development by UV irradiation.
1
In the H NMR spectra of quinone monoimines
XXIVa–XXIVc, XXVa–XXVc the singlet of the atom
H5 is present in the region 7.11–7.38 ppm, and the singlet
of the methyl protons, at 2.47– 2.51 ppm. The structure
of compounds XXIIIb, XXIIIc was established after
the oxidation to the corresponding quinone monoimines
XXVIb, XXVIc whose structure was proved by the
1H NMR spectra.
4-Amino-N-aroyl-2(3)-methylphenols IIIa–IIIc,
IVa–IVc were obtained by the reaction of 4-amino-2(3)-
methylphenols with the corresponding carboxylic acids
chlorides in the mixture DMF–AcOH, 1 : 5, in the pres-
ence of AcONa by procedure [12].
N-Aroyl-2(3)-methyl-1,4-benzoquinone mono-
imines Ia, Ib, IIb, IIc were obtained by the oxidation of
4-amino-N-aroyl-2(3)-methylphenols with Pb(OAc)4
in AcOH [12]. The products were recrystallized from
AcOH.
Analysis of the results of the halogenation of quinone
monoimines I and II and aminophenols III and IV shows
that in general the direction and the course of the haloge-
nation of quinone monoimines I and II are analogous to
those of N-arylsulfonyl-2(3)-methyl-1,4-benzoquinone
monoimines, but the presence of a strong acceptor sub-
stituent at the nitrogen atom results in some deviations.
We failed to obtain from quinone monoimines I and II
a large variety of cyclohexene structures, in particular,
products of addition of one halogen molecule, as were
obtained from the corresponding N-arylsulfonyl deriva-
tives. This is due to the stronger electron-acceptor prop-
erties of the ArCO group and consequently to the higher
C–H-acidity of protons in the ortho-position to the imine
N-(4-Bromobenzoyl)-2-methyl-1,4-benzoquinone
1
monoimine (Ia). Yield 79%, mp 116–118°C. H NMR
spectrum, δ, ppm: 2.04 d (3H, 2-Me, J 1.2 Hz), 6.66 d
(1H, H6, J 10.2 Hz), 6.85 q (1H, H3, J 2.7 Hz), 7.02–
7.06 d.d (1H, H5, J 10.2, 2.7 Hz), 7.62 d, 7.80 d (4H,
C6H4, J 8.7 Hz). Found, %: N 4.56, 4.59. C14H10BrNO2.
Calculated, %: N 4.61.
2-Methyl-N-(4-nitrobenzoyl)-1,4-benzoquinone
monoimine (Ib). Yield 71%, mp 121–123°C. 1H NMR
spectrum, δ, ppm: 2.06 d (3H, 2-Me, J 1.5 Hz), 6.70 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES...: XII.
1635
H6, J 9.6 Hz), 6.88 q (1H, H3, J 2.4 Hz), 7.05–7.08 d.d
(1H, H5, J 9.6, 2.4 Hz), 8.11 d, 8.35 d (4H, C6H4,
J 9.0 Hz). Found, %: N 10.33, 10.36. C14H10N2O4. Cal-
culated, %: N 10.37.
Br + Cl 33.79, 33.85. C14H11BrClNO2. Calculated, %:
Br + Cl 33.87.
4-Amino-2-methyl-N-(4-nitrobenzoyl)-6-chloro-
phenol (Vb). Yield 42%, mp 256–258°C. Found, %:
Cl 11.48, 11.52. C14H11ClN2O4. Calculated, %: Cl 11.56.
3-Methyl-N-(4-methylbenzoyl)-1,4-benzoquinone
1
monoimine (IIb). Yield 81%, mp 88–89°C. H NMR
N-(4-Bromobenzoyl)-2-methyl-6-chloro-1,4-benzo-
quinone monoimine (VIIa). Yield 69%, mp 128–130°C.
1H NMR spectrum, δ, ppm: 2.12 d (3H, 2-Me), 6.89 q
(1H, H3, J 2.1, 1.5 Hz), 7.25 d (1H, H5), 7.63 d, 7.80 d
(4H, C6H4, J 9.0 Hz). Found, %: Br + Cl 34.01, 34.05.
C14H9BrClNO2. Calculated, %: Br + Cl 34.07.
spectrum, δ, ppm: 2.30 d (3H, 3-Me), 2.44 s (3H,
4-Me), 6.44–6.48 d.d (1H, H6, J 2.4 Hz), 6.61 q (1H, H2,
J 1.5 Hz), 6.85 d (1H, H5, J 10.2 Hz), 7.28 d, 7.78 d (4H,
C6H4, J 8.4 Hz). Found, %: N 5.79, 5.82. C15H13NO2.
Calculated, %: N 5.85.
3-Methyl-N-(4-chlorobenzoyl)-1,4-benzoquinone
monoimine (IIc). Yield 83%, mp 112–114°C. 1H NMR
spectrum, δ, ppm: 2.29 d (3H, 3-Me), 6.47– 6.51 d.d (1H,
H6, J 2.7 Hz), 6.62 q (1H, H2, J 1.2 Hz), 6.86 d (1H, H5,
J 10.3 Hz), 7.74 d, 7.90 d (4H, C6H4, J 8.4 Hz). Found,
%: N 5.29, 5.33. C14H10ClNO2. Calculated, %: N 5.39.
2-Methyl-N-(4-nitrobenzoyl)-6-chloro-1,4-benzo-
quinone monoimine (VIIb). Yield 58%, mp 148–150°C.
1H NMR spectrum, δ, ppm: 2.14 d (3H, 2-Me), 6.92 q (1H,
H3, J 3.0, 1.5 Hz), 7.28 d (1H, H5), 8.11 d, 8.36 d (4H,
C6H4, J 9.3 Hz). Found, %: Cl 11.59, 11.62. C14H9ClNO2.
Calculated, %: Cl 11.64.
4-Amino-N-benzoyl-2-methylphenol (IIIa).
Yield 82%, mp 202–204°C. Found, %: N 6.08, 6.13.
C14H13NO2. Calculated, %: N 6.16.
N-(4-Bromobenzoyl)-2-methyl-5,6-dichloro-1,4-
benzoquinone monoimine (IXa). Yield 22%. 1H NMR
spectrum, δ, ppm: 2.06 d (3H, 2-Me), 6.82 q (1H, H3,
J 1.5 Hz), 7.61 d, 7.97 d (4H, C6H4, J 8.4 Hz).
4-Amino-2-methyl-N-(4-nitrobenzoyl)phenol
(IIIb). Yield 91%, mp 263–264°C. Found, %: N 9.93,
10.18. C14H12N2O4. Calculated, %: N 10.29.
2-Methyl-N-(4-nitrobenzoyl)-5,6-dichloro-1,4-
1
benzoquinone monoimine (IXb). H NMR spectrum,
4-Amino-2-methyl-N-(4-methylbenzoyl)phenol
(IIIc). Yield 86%, mp 228–230°C. Found, %: N 5.74,
5.79. C15H15NO2. Calculated, %: N 5.80.
δ, ppm: 2.09 d (3H, 2-Me, J 1.5 Hz), 6.86 q (1H, H3,
J 1.5 Hz), 8.12 d, 8.37 d (4H, C6H4, J 8.4 Hz).
2-Methyl-N-(4-methylbenzoyl)-5,6-dichloro-1,4-
benzoquinone monoimine (IXc). Yield 72%, mp 149–
150°C. 1H NMR spectrum, δ, ppm: 2.04 d (3H, 2-Me),
2.45 s (3H, 4-MeC6H4), 6.82 q (1H, H3, J 1.5 Hz), 7.29 d,
7.82 d (4H, C6H4, J 8.4 Hz). Found, %: Cl 22.97, 23.00.
C15H11Cl2NO2. Calculated, %: Cl 23.01.
4-Amino-N-benzoyl-3-methylphenol (IVa). Yield
89%, mp 202–204°C. Found, %: N 6.09, 6.14. C14H13NO2.
Calculated, %: N 6.16.
4-Amino-3-methyl-N-(4-methylbenzoyl)phenol
(IVb). Yield 75%, mp 208–210°C. Found, %: N 5.71,
5.77. C15H15NO2. Calculated, %: N 5.80.
N-Benzoyl-2-methyl-5,6-dichloro-1,4-benzoqui-
none monoimine (IXd). Yield 79%, mp 92–94°C.
1H NMR spectrum, δ, ppm: 2.05 d (3H, 2-Me), 6.83 q
(1H, H3, J 1.8 Hz), 7.49–7.93 m (5H, Ph). Found, %:
Cl 24.06, 24.09. C14H9Cl2NO2. Calculated, %: Cl 24.11.
4-Amino-3-methyl-N-(4-chlorobenzoyl)phenol
(IVc). Yield 81%, mp 205–206°C. Found, %: N 5.30,
5.34. C14H12ClNO2. Calculated, %: N 5.35.
Chlorination of quinone monoimines Ia, Ib, IIb,
IIc and aminophenols IIIa–IIIc, IVa–IVc. Through the
solution of 2 mmol of compounds under study in 3 ml
CHCl3,AcOH, DMF, or a mixture DMF–AcOH, 1 : 5, was
passes a flow of dry chlorine at the rate 15–20 ml min–1
at 25–30°C. The ratio initial compound–chlorine was
monitored by the weight gain, and it was varied in the
range from 1 : 1 to 1 : 6.5. After several hours the reac-
tion products were filtered off and recrystallized from
acetic acid.
N-(4-Bromobenzoyl)-2-methyl-3,6-dichloro-1,4-
1
benzoquinone monoimine (Xa). Yield 78%. H NMR
spectrum, δ, ppm: 2.33 s (3H, 2-Me), 7.16 s (1H, H5),
7.64 d, 7.81 d (4H, C6H4, J 8.7 Hz).
2-Methyl-N-(4-nitrobenzoyl)-3,6-dichloro-1,4-
benzoquinone monoimine (Xb). 1H NMR spectrum, δ,
ppm: 2.35 s (3H, Me2), 7.21 s (1H, H5), 8.12 d, 8.37 d
(4H, C6H4, J 9.0 Hz).
N-Benzoyl-2-methyl-3,6-dichloro-1,4-benzoqui-
none monoimine (Xc). 1H NMR spectrum, δ, ppm: 2.10 s
(3H, 2-Me), 7.17 s (1H, H5), 7.49–7.93 m (5H, Ph).
4-Amino-N-(4-bromobenzoyl)-2-methyl-6-chloro-
phenol (Va). Yield 84%, mp 160–162°C. Found, %:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

AVDEENKO et al.
1636
4-Amino-N-benzoyl-2-methyl-5,6-dichlorophenol
(XIa). Yield 74%, mp 221–222°C. Found, %: Cl 23.86,
4-Amino-3-methyl-6-chloro-N-(4-chlorobenzoyl)
phenol (XIXc). Yield 80%, mp 204–206°C. H NMR
1
spectrum, δ, ppm: 2.13 s (3H, 3-Me), 6.87 s (1H, H2),
7.28 s (1H, H5), 7.60 d, 7.98 d (4H, C6H4, J 8.1 Hz).
Found, %: Cl 23.88, 23.93. C14H11Cl2NO2. Calculated,
%: Cl 23.94.
23.91. C14H11Cl2NO2. Calculated, %: Cl 23.94.
4-Amino-2-methyl-N-(4-nitrobenzoyl)-5,6-dichlo-
rophenol (XIb). Yield 80%, mp 244–246°C. Found, %:
Cl 19.96, 21.03. C14H10Cl2N2O4. Calculated, %: Cl 20.78.
4-Amino-N-benzoyl-3-methyl-2,6-dichlorophenol
(XXIa). Yield 69%, mp 206–208°C. Found, %: Cl 23.89,
23.92. C14H11Cl2NO2. Calculated, %: Cl 23.94.
4-Amino-2-methyl-N-(4-methylbenzoyl)-5,6-
dichlorophenol (XIc). Yield 66%, mp 210–212°C.
Found, %: Cl 22.77, 22.83. C15H13Cl2NO2. Calculated,
%: Cl 22.86.
4-Amino-3-methyl-N-(4-methylbenzoyl)-2,6-
dichlorophenol (XXIb). Yield 77%, mp 208–210°C.
Found, %: Cl 22.80, 22.84. C15H13Cl2NO2. Calculated,
%: Cl 22.86.
4-Benzoylimino-6-methyl-2,3,5,6-tetrachloro-
cyclohex-2-en-1-one (XVa). Yield 13%, mp 100–102°C.
1H NMR spectrum, δ, ppm: 1.90 s (3H, 6-Me), 5.01 s (1H,
H5), 7.49–7.98 m (5H, Ph). 13C NMR spectrum, δ, ppm:
22.59 (6-Me), 57.88 (C5), 64.81 (C6), 129.04 (C2′), 129.81
(C3′), 131.23 (C1′), 134.67 (C4′), 138.30 (C2), 142.71 (C3),
154.24 (C4), 177.36 (C=Oaroyl), 180.27 (C1). Found, %:
Cl 38.79, 38.84. C14H9Cl4NO2. Calculated, %: Cl 38.85.
4-Amino-3-methyl-2,6-dichloro-N-(4-chlorobenzo-
yl)phenol (XXIc). Yield 50%, mp 206–208°C. Found, %:
Cl 32.13, 32.15. C14H10Cl3NO2. Calculated, %: Cl 32.17.
N-Benzoyl-3-methyl-2,6-dichloro-1,4-benzoqui-
none monoimine (XXIVa). Yield 60%, mp 107–109°C.
1H NMR spectrum, δ, ppm: 2.48 s (3H, 3-Me), 7.13 s (1H,
H5), 7.49–7.90 m (5H, Ph). Found, %: Cl 24.08, 24.10.
C14H9Cl2NO2. Calculated, %: Cl 24.11.
6-Methyl-4-(4-nitrobenzoyl)imino-2,3,5,6-tetra-
chlorocyclohex-2-en-1-one (XVb). Yield 55%, mp 153–
1
154°C. H NMR spectrum, δ, ppm: 1.93 s (3H, 6-Me),
3-Methyl-N-(4-methylbenzoyl)-2,6-dichloro-1,4-
benzoquinone monoimine (XXIVb). Yield 63%, mp
5.03 s (1H, H5), 8.14 d, 8.38 d (4H, C6H4, J 9.0 Hz).
Found, %: Cl 33.92, 35.06. C14H8Cl4N2O4. Calculated,
%: Cl 34.58.
1
150–152°C. H NMR spectrum, δ, ppm: 2.45 s (3H,
4-Me), 2.48 s (3H, 3-Me), 7.11 s (1H, H5), 7.30 d,
7.78 d (4H, C6H4, J 8.1 Hz). Found, %: Cl 22.97, 23.00.
C15H11Cl2NO2. Calculated, %: Cl 23.01.
2-Methyl-N-(4-nitrobenzoyl)-3,5,6-trichloro-1,4-
benzoquinone monoimine (XVIb). 1H NMR spectrum,
δ, ppm: 2.22 s (3H, 2-Me), 8.04 d, 8.38 d (4H, C6H4,
J 8.7 Hz).
3-Methyl-2,6-dichloro-N-(4-chlorobenzoyl)-1,4-
benzoquinone monoimine (XXIVc). Yield 71%, mp
2-Methyl-N-(4-methylbenzoyl)-3,5,6-trichloro-1,4-
benzoquinone monoimine (XVIc). Yield 70%, mp 210–
1
158–160°C. H NMR spectrum, δ, ppm: 2.47 s (3H,
3-Me), 7.12 s (1H, H5), 7.48 d, 7.85 d (4H, C6H4,
J 8.4 Hz). Found, %: Cl 32.30, 32.35. C14H8Cl3NO2.
Calculated, %: Cl 32.37.
1
212°C. H NMR spectrum, δ, ppm: 2.27 s (3H, 2-Me),
2.44 (3H, 4-Me), 7.28 d, 7.73 d (4H, C6H4, J 8.1 Hz).
13C NMR spectrum, δ, ppm: 21.77 (4’-Me), 23.15 (2-
Me), 128.72 (C2′), 129.18 (C1′), 129.56 (C3′), 138.74
(C6), 138.81 (C5), 139.02 (C3), 143.74 (C4), 144.59 (C4′),
144.60 (C2), 175.27 (C=Oaroyl), 175.46 (C1). Found, %:
Cl 30.99, 31.01. C15H10Cl3NO2. Calculated, %: Cl 31.04.
N-Benzoyl-3-methyl-2,5,6-trichloro-1,4-benzo-
quinone monoimine (XXVIa). Yield 81%, mp 194–
1
196°C. H NMR spectrum, δ, ppm: 2.46 s (3H, 3-Me),
7.48–7.82 m (5H, Ph). 13C NMR spectrum, δ, ppm: 17.16
(3-Me), 128.66 (C2′), 128.93 (C3′), 131.77 (C1′), 133.72
(C4′), 137.32 (C2), 137.36 (C6), 138.92 (C5), 144.05 (C3),
147.17 (C4), 170.64 (C1), 175.41 (C=Oaroyl). Found, %:
Cl 32.29, 32.35. C14H8Cl3NO2. Calculated, %: Cl 32.37.
6-Methyl-4-(4-methylbenzoyl)imino-2,3,5,5,6-
pentachlorocyclohex-2-en-1-one (XVII). Yield 70%,
mp 112–114°C. 1H NMR spectrum, δ, ppm: 2.18 s (3H,
6-Me), 2.44 s (3H, 4-Me), 7.29 d, 7.77 d (4H, C6H4,
J 8.1 Hz). 13C NMR spectrum, δ, ppm: 20.55 (6-Me),
21.75 (4’-Me), 72.27 (C6), 88.77 (C5), 128.82 (C2′),
129.04 (C1′), 129.58 (C3′), 138.17(C2), 138.84 (C3),
144.80 (C4′), 147.53 (C4), 173.97 (C1), 178.61 (C=Oaroyl).
Found, %: Cl 42.81, 42.85. C15H10Cl5NO2. Calculated,
%: Cl 42.87.
3-Methyl-N-(4-methylbenzoyl)-2,5,6-trichloro-
1,4-benzoquinone monoimine (XXVIb). Yield 50%,
mp 200–202°C. 1H NMR spectrum, δ, ppm: 2.44 s (3H,
4-Me), 2.45 s (3H, 3-Me), 7.28 d, 7.70 d (4H, C6H4,
J 8.1 Hz). 13C NMR spectrum, δ, ppm: 17.18 (3-Me),
21.77 (4′-Me), 128.72 (C2′), 129.07 (C1′), 129.66 (C3′),
144.76 (C4′), 137.22 (C2), 137.49 (C6), 138.83 (C5),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES...: XII.
1637
144.76 (C3), 147.00 (C4), 170.70 (C1), 175.46 (C=Oaroyl).
41.71. C14H9Br2NO2. CычandCлe-HO, %: Br 41.72.
Found, %: Cl 30.96, 31.03. C15H10Cl3NO2. Calculated,
%: Cl 31.04.
6-Bromo-2-methyl-N-(4-nitrobenzoyl)-1,4-ben-
zoquinone monoimine (VIIIb). Yield 61%, mp 170–
172°C. H NMR spectrum, δ, ppm: 2.14 d (3H, 2-Me,
J 1.8 Hz), 6.93 q (1H, H3, J 1.8 Hz), 7.55 d (1H, H5,
J 2.1 Hz), 8.11 d, 8.36 d (4H, C6H4, J 8.7 Hz). Found, %:
Br 22.16, 23.09. C14H9BrN2O4. Calculated, %: Br 22.89.
1
3-Methyl-2,5,6-trichloro-N-(4-chlorobenzoyl)-
1,4-benzoquinone monoimine (XXVIc). Yield 43%,
mp 198–200°C. 1H NMR spectrum, δ, ppm: 2.45 s (3H,
3-Me), 7.47 d, 7.76 d (4H, C6H4, J 8.4 Hz). Found, %:
Cl 39.01, 39.05. C14H7Cl4NO2. Calculated, %: Cl 39.06.
4-Amino-N-benzoyl-5,6-dibromo-2-methylphenol
(XIIa). Yield 94%, mp 200–202°C. Found, %: Br 41.46,
41.48. C14H11Br2NO2. Calculated, %: Br 41.50.
4-Benzoylimino-5-methyl-2,3,5,6,6-pentachlo-
rocyclohex-2-en-1-one (XXVIIa). Yield 36%, mp
1
98–100°C. H NMR spectrum, δ, ppm: 2.30 s (3H,
4-Amino-5,6-dibromo-2-methyl-N-(4-methylben-
zoyl)phenol (XIIc). Yield 95%, mp 224–226°C. Found,
%: Br 39.98, 40.01. C15H13Br2NO2. Calculated, %:
Br 40.04.
5-Me), 7.49–7.85 m (5H, Ph). Found, %: Cl 44.32, 44.35.
C14H8Cl5NO2. Calculated, %: Cl 44.37.
5-Methyl-4-(4-methylbenzoyl)imino-2,3,5,6,6-
pentachlorocyclohex-2-en-1-one (XXVIIb). Yield 56%,
mp 110–112°C. 1H NMR spectrum, δ, ppm: 2.29 s (3H,
5-Me), 2.44 s (3H, 4-Me), 7.29 d, 7.73 d (4H, C6H4,
N-Benzoyl-5,6-dibromo-2-methyl-1,4-benzoqui-
none monoimine (XIIIa). Yield 63%, mp 114–116°C.
1H NMR spectrum, δ, ppm: 2.05 d (3H, 2-Me), 6.88 q
(1H, H3, J 1.8 Hz), 7.49–7.93 m (5H, Ph). Found, %:
Br 41.67, 41.70. C14H9Br2NO2. Calculated, %: Br 41.72.
13
J 8.1 Hz). C NMR spectrum, δ, ppm: 21.77 (4’-Me),
23.15 (5-Me), 74.51 (C5), 88.40 (C6), 128.79 (C2′), 129.15
(C1′), 129.67 (C3′), 136.81 (C2), 139.67 (C3), 144.90 (C4′),
150.56 (C4), 174.55 (C=Oaroyl), 174.18 (C1). Found, %:
Cl 42.79, 42.85. C15H10Cl5NO2. Calculated, %: Cl 42.87.
5,6-Dibromo-2-methyl-N-(4-methylbenzoyl)-1,4-
benzoquinone monoimine (XIIIc). Yield 69%, mp
1
155–156°C. H NMR spectrum, δ, ppm: 2.04 d (3H,
5-Methyl-4-(4-chlorobenzoyl)imino-2,3,5,6,6-
pentachlorocyclohex-2-en-1-one (XXVIIc). Yield 59%,
mp 103–104°C. 1H NMR spectrum, δ, ppm: 2.29 s (3H,
5-Me), 7.48 d, 7.78 d (4H, C6H4, J 8.7 Hz). Found, %:
Cl 48.13, 49.51. C14H7Cl6NO2 Calculated, %: Cl 49.02.
2-Me, J 1.5 Hz), 2.44 s (3H, 4-Me), 6.87 q (1H, H3),
7.29 d, 7.81 d (4H, C6H4, J 8.4 Hz). Found, %: Br 40.19,
40.23. C15H11Br2NO2. Calculated, %: Br 40.25.
5-Benzoyloxy-2,3,6-tribromo-6-methyl-cyclohex-
2-en-1,4-dione (XVIII). Yield 15%, mp 156–158°C.
1H NMR spectrum, δ, ppm: 2.01 s (3H, 6-Me), 6.20 s (1H,
H5), 7.45–7.95 m (5H, Ph). 13C NMR spectrum, δ, ppm:
23.36 (6-Me), 56.65 (C6), 77.18 (C5), 127.48 (C1′), 128.83
(C2′), 130.11 (C3′), 134.42 (C4′), 137.80 (C3), 146.12 (C2),
175.15 (C=Oaroyl), 180.33 (C4), 181.46 (C1). Found, %:
Br 49.01, 50.19. C14H9Br3O4. Calculated, %: Br 49.84.
Bromination of compounds Ia, Ib, IIb, IIc, IIIa–
IIIc, IVa–IVc. To a solution of 2 mmol of compound
under study in 3 ml of CHCl3, AcOH, DMF, or the mix-
ture DMF–AcOH, 1 : 5, was added dropwise at stirring
a solution of bromine in the corresponding solvent till the
necessary ratio initial substance–bromine was attained
(1 : 1, 1 : 3, 1 : 5, 1 : 10). After several hours the reaction
products were filtered off, washed with acetic acid, and
recrystallized from acetic acid.
4-Amino-N-benzoyl-6-dibromo-3-methylphenol
(XXa). Yield 37%, mp 247–249°C. Found, %: Br 26.11,
26.13. C14H12BrNO2. Calculated, %: Br 26.14.
4-Amino-6-bromo-N-(4-bromobenzoyl)-2-meth-
ylphenol (VIa). Yield 63%, mp 228–230°C. Found, %:
Br 41.44, 41.49. C14H11Br2NO2. Calculated, %: Br 41.50.
4-Amino-N-benzoyl-2,6-dibromo-3-methylphenol
(XXIIa). Yield 59%, mp 208–210°C. Found, %: Br 41.42,
41.46. C14H11Br2NO2. Calculated, %: Br 41.50.
4-Amino-6-bromo-N-(4-nitrobenzoyl)-2-methyl-
phenol (VIb). Yield 59%, mp 262–263°C. Found, %:
Br 22.61, 23.10. C14H11BrN2O4. Calculated, %: Br 22.75.
4-Amino-2,6-dibromo-3-methyl-N-(4-methyl-
benzoyl)phenol (XXIIb). Yield 78%, mp 217–218°C.
Found, %: Br 39.96, 40.02. C15H13Br2NO2. Calculated,
%: Br 40.04.
6-Bromo-N-(4-bromobenzoyl)-2-methyl-1,4-benzo-
quinone monoimine (VIIIa).Yield 55%, mp 150–152°C.
1H NMR spectrum, δ, ppm: 2.11 d (3H, 2-Me, J 1.8 Hz),
6.89 q (1H, H3, J 1.8 Hz), 7.52 d (1H, H5, J 2.4 Hz),
7.63 d, 7.80 d (4H, C6H4, J 9.0 Hz). Found, %: Br 41.69,
4-Amino-2,6-dibromo-3-methyl-N-(4-chlorobenzo-
yl)phenol (XXIIc). Yield 75%, mp 246–248°C. Found,
%: Br + Cl 46.50, 46.52. C14H10Br2ClNO2. Calculated,
%: Br + Cl 46.54.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

AVDEENKO et al.
1638
4. Avdeenko, A.P., Konovalova, S.A., Il’chenko, A.Ya.
N-Benzoyl-2,6-dibromo-3-methyl-1,4-benzoqui-
Glinyanaya, N.M., Zh. Org. Khim., 2006, vol. 42, p. 64;
Avdeenko, A.P., and Konovalova, S.A., Zh. Org. Khim.,
2006, vol. 42, p. 689.
none monoimine (XXVa). Yield 63%, mp 120–122°C.
1H NMR spectrum, δ, ppm: 2.51 s (3H, 3-Me), 7.39 s (1H,
H5), 7.49–7.90 m (5H, Ph). Found, %: Br 41.69, 41.73.
C14H9Br2NO2. Calculated, %: Br 41.72.
5. Avdeenko, A.P., Marchenko, I.L., Kostygova, N.V. Ukr.
Khim. Zh., 2001, vol. 67, p. 43; Avdeenko, A.P., and
Marchenko, I.L., Zh. Org. Khim., 2001, vol. 37, p. 869;
Avdeenko, A.P., Marchenko, I.L., Yusina, A.L., Kon-
ovalova, S.A., and Ludchenko, O.N., Zh. Org. Khim., 2005,
vol. 41, p. 1824.
6. Avdeenko, A.P., Pirozhenko, V.V., Shishkin, O.V., Shish-
kina, S.V., Konovalova, S.A., and Ludchenko, O.N.,
Zh. Org. Khim., 2008, vol. 44, p. 547; Avdeenko, A.P.,
Pirozhenko, V.V., Shishkin, O.V., Palamarchuk, G.V.,
Zubatyuk, R.I., Konovalova, S.A., and Ludchenko, O.N.,
Zh. Org. Khim., 2008, vol. 44, p. 818.
7. Avdeenko,A.P., Konovalova, S.A., Ludchenko, O.N., Pala-
marchuk, G.V., and Shishkin, O.V., Zh. Org. Khim., 2009,
vol. 45, p. 1660; Avdeenko, A.P., Konovalova, S.A., and
Ludchenko, O.N., Zh. Org. Khim., 2009, vol. 45, p. 1804.
8. Fernando, R.C. and Calder, C., Austral. J. Chem., 1980,
vol. 33, p. 2299.
2,6-Dibromo-3-methyl-N-(4-methylbenzoyl)-1,4-
benzoquinone monoimine (XXVb). Yield 48%, mp
1
160–162°C. H NMR spectrum, δ, ppm: 2.45 s (3H,
4-Me), 2.51 s (3H, 3-Me), 7.37 s (1H, H5), 7.32 d, 7.78 d
(4H, C6H4, J 8.1 Hz). Found, %: Br 40.19, 40.23. C15H-
11Br2NO2. Calculated, %: Br 40.25.
2,6-Dibromo-3-methyl-N-(4-chlorobenzoyl)-1,4-
benzoquinone monoimine (XXVc). Yield 65%, mp 140–
1
142°C. H NMR spectrum, δ, ppm: 2.50 s (3H, 3-Me),
7.38 s (1H, H5), 7.48 d, 7.85 d (4H, C6H4, J 8.7 Hz).
Found, %: Br + Cl 46.74, 46.76. C14H8Br2ClNO2. Cal-
culated, %: Br + Cl 46.77.
REFERENCES
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010