Hydrohalogenation of N-acetyl(aroyl)-1,4-benzoquinone monoimines

Article abstract of DOI:10.1134/S1070428011020102

New N-acetyl-1,4-benzoquinone monoimines alkyl-substituted in the quinoid ring were synthesized. The hydrohalogenation of N-acetyl(aroyl)-1,4-benzoquinone monoimines proceeds exclusively in keeping with the 1,4-addition. The hydrochlorination occurs along the ionic mechanism, in the hydrobromination grows the role of the radical mechanism.

Full text of DOI:10.1134/S1070428011020102

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 2, pp. 214229. Pleiades Publishing, Ltd., 2011.
Original Russian Text  A.P. Avdeenko, S.A. Konovalova, O.N. Ludchenko, O.P. Ledeneva, A.V. Vakulenko, 2011, published in Zhurnal Organicheskoi Khimii,
2011, Vol. 47, No. 2, pp. 223237.
Hydrohalogenation
of N-Acetyl(aroyl)-1,4-benzoquinone Monoimines
A. P. Avdeenkoa, S. A. Konovalovaa, O. N. Ludchenkoa,
O. P. Ledenevaa, and A. V. Vakulenkob
aDonbass State Machinebuilding Academy, Kramatorsk-13, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
bCenter of Heterocyclic Compounds, University of Florida, Gainesville, USA
Received July 13, 2010
Abstract—New N-acetyl-1,4-benzoquinone monoimines alkyl-substituted in the quinoid ring were synthesized.
The hydrohalogenation of N-acetyl(aroyl)-1,4-benzoquinone monoimines proceeds exclusively in keeping with
the 1,4-addition. The hydrochlorination occurs along the ionic mechanism, in the hydrobromination grows the
role of the radical mechanism.
DOI: 10.1134/S1070428011020102
The hydrohalogenation of versatile N-substituted
p-quinone monoimines is fairly well understood [1–3].
The halogen addition occurs mostly into the positions 2
and 6 of the quinoid ring by the 1,4-addition scheme [1,
2]. In the case of N-aryl-1,4-benzoquinone monoimines
depending on the substituent in the para-position of the
aryl fragment the halogen atom enters into the position 2
or 3 of the quinoid ring by the route of 1,4- or 6.3-addi-
tion [3]. In describing the orientation of the nucleophile
addition to quinone imines the following numeration of
the atoms in the quinone imine molecule is applied: The
first digit indicates the atom adding the proton (or another
electrophile), the second digit determines the atom adding
the acid anion (or another nucleophil) [4].
thiols [9], dimethylamine [10], and halogens [11]. The
other investigated reactions were the halogenation of
4-amino-N-acetylphenol [12], reactions of N-acetyl-
2,6(3,5)-dimethyl-1,4-benzoquinone monoimines with
aniline, ethanol, water, hydrogen chloride, ethanethiol
[13]. It was established that the reactions of N-acetyl-
1,4-benzoquinone imine with dimethylamine [10], thi-
ols [9] and of N-acetyl-3,5-dimethyl-1,4-benzoquinone
monoimine with hydrogen chloride and ethanethiol [13]
followed the scheme of the 1,4-addition, and the N-acetyl-
2,6-dimethyl-1,4-benzoquinone monoimine reacted with
hydrogen chloride along the 6,3-addition path [13]. The
hydrohalogenation of unsubstituted in the quinoid ring,
monoalkyl, and 2,5-dialkyl-substituted N-acetyl-1,4-
benzoquinone monoimines was not examined.
4
3
4-Amino-N-aroylphenols are close analogs of
paracetamol, and they are also tested for pharma-
ceuticals [14]. Their oxidation leads to the formation
of N-aroyl-1,4-benzoquinone monoimines whose
reactivity is fairly well studied. The reactions of various
N-aroyl-1,4-benzoquinone monoimines with halogens
[15], sodium arylsulfinates [16], and potassium thiocya-
nate [17] were investigated. Yet the hydrohalogenation
of unsubstituted in the quinoid ring and monoalkyl-
substituted N-aroyl-1,4-benzoquinone monoimines due
to their instability was not previously studied.
2
5
X N
6O
1
The 4-amino-N-acetylphenol (paracetamol) is an
efficient analgesic, and its oxidation product, N-acetyl-
1,4-benzoquinone imine, is an intermediate compound in
the chain of transformations leading to the hepatotoxicity
of the paracetamol [5]. In this connection large number
of publications concerns the study of the oxidation of
4-amino-N-acetylphenol to N-acetyl-1,4-benzoquinone
imine [6, 7] and the reactivity of N-acetyl-1,4-benzo-
quinone imine with respect to biological objects [8],
It was previously suggested that the hydrochlorination
214

HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
215
of the N-acetyl(aroyl)-1,4-benzoquinone monoimines
unsubstituted in the quinoid ring might proceed both as
1,4- and 6,3-addition [18]. Therefore the goal of the pres-
ent research was the establishment of the direction of the
halogen addition in the hydrohalogenation of N-aroyl- and
N-acetyl-1,4-benzoquinone monoimines.
-3-chlorophenols V and VI treated with acetyl(aroyl)
chlorides 4-amino-N-acetyl(aroyl)-2-chloro- and
-3-chlorophenols IIIa–IIIf and IVa–IVf (Scheme 1).
The analysis of the 1H NMR spectra of the products of
hydrochlorination of quinone imines IIa–IIf showed that
only 4-amino-N-acetyl(aroyl)-2-chlorophenols IIIa–IIIf
formed, and no products of 6,3-addition, aminophenols
IVa–IVf, were detected (Scheme 1), but the reaction
mixtures contained impurities of the reduced forms of
quinone monoimines, aminophenols Ia–If, and hydrolysis
products.
N-Acetyl(aroyl)-1,4-benzoquinone monoimines IIa–
IIf were obtained in situ by the oxidation of 4-amino-
N-acetyl(aroyl)phenols Ia–If (Scheme 1). Chloroform
was used as solvent during the oxidation. The solvent
was selected to provide a good solubility of quinone
imines IIa–IIf without their decomposition which was
observed in acetone and acetic acid. On the other hand,
initial 4-amino-N-acetyl(aroyl)phenols Ia–If are insoluble
in chloroform that simplifies thair separation from the
obtained quinone imines. The oxidation of aminophenols
Ia–If was performed with silver(I) oxide. The application
to this end of lead tetraacetate gave unsuitable results. The
formation of quinone monoimines IIa–IIf was proved
by the IR spectra of the obtaind solutions of quinone
imines. The IR spectra contained the absorption band
characteristic of groups C=O, C=N (1650, 1580 cm–1)
and lacked the absorption in the region 3200–3500 cm–1
characteristic of groups NH, OH.
Aiming at elucidation of the hydrochlorination mecha-
nism of compounds IIa–IIf we performed quantum-
chemical calculations. For quinone monoimines IIa and
IId by method DFT (B3LYP) with the use of basis set
6-31+G(d) a complete optimization was carried out of all
geometric parameters of initial quinone monoimines and
probable transition states that might form in the course
of the hydrochlorination.
Proceeding from [19, 20] a conclusion is presum-
able that in the hydrohalogenation of the N-substituted
1,4-benzoquinone monoimines the transition states may
be either anion-radical, radical, or protonated species.
The hydrogen chloride is not prone to the formation
of radical species [21], therefore the hydrochlorination
apparently proceeds through the protonation of the initial
quinone monoimine.
The hydrochlorination was carried out by passing
the gaseous hydrogen chloride through the chloroform
solution of quinone imines IIa–IIf. The hydrochlorination
products were filtered off and in order to detect all
possible reaction products their NMR spectra were
registered without additional purification. To ensure the
precise identification of compounds by an independent
synthesis we obtained from 4-amino-2-chloro- and
In the first stage the initial quinone monoimine un-
dergoes protonation, and depending on the properties of
the substituent at the nitrogen it may occur both at the
nitrogen and the oxygen [20]. According to the calcula-
Scheme 1.
Cl
Cl
XCOCl
NH
OH
OH
OH
H2N
X C
O
HCl
V
III a–IIIf
Cl
[O]
NH
OH
O
N
Cl
X C
O
X C
O
HCl
XCOCl
NH
OH
H2N
X C
O
Ia–If
IIa–IIf
IV a–IVf
X = Me (a), 4-MeOC6H4 (b), 4-MeC6H4 (c), Ph (d), 4-ClC6H4 (e), 4-NO2C6H4 (f).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011
VI

AVDEENKO et al.
216
1,4-benzoquinone monoimines first occurs the protonation
of the more basic nitrogen atom, and then the addition of
the chloride anion to the ortho-position of the carbonyl
carbon atom. The addition of the chloride anion to the
ortho-position with respect to the imine carbon atom is
unfavorable by the energy, therefore the hydrochlorina-
tion of the N-acetyl(aroyl)-1,4-benzoquinone monoimines
yields only the products of 1,4-addition.
tions in the event of imines IIa–IIf the protonation at the
nitrogen atom is more favorable (Scheme 2) than at the
oxygen atom. The energy of the protonated form A of
quinone monoimine IIa attains –514.58628, of quinone
monoimine IId, –706.34282 a.u., of the protonated form
B of quinone monoimine IIa, –514.57866, of quinone
monoimine IId, –706.32120 a.u. Namely, for quinone
monoimine IIa the energy of the transition state A is less
than the energy of the form B protonated at the oxygen
atom by 20 kJ mol−1, and for quinone monoimine IId,
by 56.8 kJ mol−1.
The N-acetyl(aroyl)-1,4-benzoquinone monoimines
containing a single methyl group in the quinoid ring
are more stable compounds than the unsubstituted
acetyl(aroyl) derivatives due to their reduced redox poten-
tial [22]. They have in the quinoid ring a free C=C bond
excluding the effect of the steric factor on the halide ion
addition to the carbon atom of this bond.
In the second stage the chloride anion adds to cation
A. In keeping with the calculations, the energies of the
possible transition states C–F (with accounting for the
spatial position of the CO group with respect to the ring)
are at X = Me: –975.06881(C), –97.06827 (D), –975.1035
(E), –974.98688 (F) a.u., and at X = Ph: –1166.81199
(C), – 1166.81139 (D), –1166.75576 (E), –116.73110 (F)
a.u.. Hence from the energy viewpoint the structures C,
D (Scheme 2) are more favorable, and their energies are
virtually equal [the difference 1.4 (X = Me), 1.6 kJ mol−1
(X = Ph)], whereas the energy of structure E exceeds that
of structure D by 152.1 (X = Me), 140.6 kJ mol− (X = Ph),
and the energy of structure F exceeds that of structure C
by 215.1 (X = Me), 212.4 kJ mol−1 (X = Ph).
N-Acetyl(aroyl)-2-methyl- and -3-methyl-1,4-benzo-
quinone monoimines VIIIa–VIIIf, Xa–Xf were obtained
by oxidation of the corresponding 4-aminomethylphenols
VIIa–VIIf, IXa–IXf (Scheme 3). We succeeded to isolate
in the crystalline state quinone monoimines VIIIe,VIIIf,
Xa–Xc, Xe. The formation in the solution of quinone
monoimines VIIIa–VIIId, Xd was proved by IR spectra.
In contrast to N-arylsulfonyl-2-methyl-1,4-benzo-
quinone monoimines [23] existing in solution as two
1
isomers in the H NMR spectra of N-aroyl derivatives
Hence at the hydrochlorination of the N-acetyl(aroyl)-
VIIIe and VIIIf a single set of signals is present. It was
Scheme 2.
H
N
O
X
X
_
Cl
O
+Cl
H
C
H
Cl
_
H
H
N
+Cl
N
O
O
H+
O
X
X
+
D
O
Cl
A
H
N
O
H
H+
X
N
O
O
O
X
X
N
OH
O
II
E
+
O
H
B
N
O
H
Cl
F
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
217
Scheme 3.
Me
Me
OH
Me
OH
Me
[O]
[O]
HHlg
O
NH
N
NH
O
N
C
O
X
C
O
C
O
X
X
C
O
X
Hlg
Hlg
XIa–XIf, XIIa–XIIf
VIIIa–VIIIf
XIIIb–XIIIf, XIVe, XIVf
VIIa–VIIf
X = Me (a), 4-MeOC6H4 (b), 4-MeC6H4 (c), Ph (d), 4-BrC6H4 (e), 4-NO2C6H4 (f); Hlg = Cl (XI, XIII), Br (XII, XIV).
VIIId. In the 1H NMR spectra of quinone monoimines
XIIIb–XIIIf, XIVe, XIVf a quartet of atom H3 is observed
in the region δ 6.92 and 6.89 ppm and a doublet of atom
H5 with the meta-coupling constant in the region δ 7.25
and 7.52 ppm, confirming the structure of imines.
formerly established that N-aroyl-1,4-benzoquinone
monoimines have lower barrier to the Z,E-isomerization
(∆G≠298K 44–46 kJ mol−1) [24] than the arylsulfonyl
derivatives (∆G≠298K 65–80 kJ mol−1) [25]. Therefore in
the solutions of compounds VIIIa–VIIIf already at the
room temperature fast Z,E-isomerization occurred, and
notwithstanding the existence of two isomeric forms the
1H NMR spectra contain a single set of signals.
The hydrohalogenation of quinone monoimines
Xa–Xf provided two isomers: 4-amino-N-acetyl(aroyl)-
6-halo- (XVa–XVf, XVIb–XVIf) and -2-halo-3-methyl-
phenols (XVIIa–XVIIf, XVIIIb–XVIIIf), also forming
by 1,4-addition (Scheme 4). The reaction products were
analyzed by 1H NMR without preliminary purification. In
the 1H NMR spectra of aminophenols XVa–XVf, XVIb–
XVIf two singlet signals of atoms H2 and H5 were ob-
served at δ 6.85 and 7.27 ppm respectively. The 1H NMR
spectra of aminophenols XVIIa–XVIIf, XVIIIb–XVIIIf
are characterized by the presence of two doublets with the
ortho-coupling constant, δ 6.83 (H6) and 7.04 (H5) ppm.
The similar regioselective addition of hydrogen halides
was previously observed in the hydrohalogenation of the
N-arylsulfonyl-3-methyl-1,4-benzoquinone monoimines
[23]. In the hydrobromination of imine Xa 2,6-dibromo
derivative XIX was also isolated.
The hydrochlorination of quinone monoimines VIIIa–
VIIIf, Xa–Xf was performed with gaseous hydrogen
chloride in chloroform, the hydrobromination, in AcOH
by adding an equimolar amount of 40% HBr.
The hydrochlorination of quinone monoimines VIIIa–
VIIId, Xd was carried out without their isolqation from
the solution just after the oxidation of the corresponding
aminophenols VIIa–VIId, IXd with silver(I) oxide in
chloroform, and the hydrobromination was performed
after oxidation with lead tetraacetate in AcOH.
The experiment demonstrated that the hydrohaloge-
nation of quinone monoimines VIIIa–VIIIf afforded
only the products of 1,4-addition XIa–XIf, XIIb–XIIf
(Scheme 3) as in the case of the corresponding N-aryl-
sulfonyl derivatives [23]. No products of 6,3-addition
were detected. We failed to isolate the reaction product
of the hydrobromination of N-acetyl-2-methyl-1,4-
benzoquinone monoimine (VIIIa), only the hydrolysis
products were obtained. In the 1H NMR spectra of com-
pounds XIa–XIf, XIIb–XIIf two characteristic doublets
were observed at δ 7.43–7.48 and 7.71–7.86 ppm with
the meta-coupling constant which corresponded to atoms
H3 and H5.
1
The analysis of the H NMR spectra of the reaction
products showed that nearly in all cases in the mixtures
6-halo derivatives XVa–XVf, XVIb–XVIf prevailed (see
the table), therewith at the hydrobromination the content
of the second isomer, 2-bromo derivative XVIIIb–XVIIIf
was higher than at the hydrochlorination, especially in
the case of N-(4-nitrobenzoyl)-substituted imine Xf. It
indicates that the steric factor (the presence of Me group
at the C=C bond of the quinoid ring) does not significantly
affect the hydrohalogenation of imines Xa–Xf.
In order to prove the structure of aminophenols XIa–
XIf, XIIb–XIIf they were oxidized with lead tetraacetate
in acetic acid into the corresponding quinone monoimines
XIIIb–XIIIf, XIVe, XIVf. We did not succeed in isolat-
ing quinone monoimines XIIIa, XIVa–XIVd in the crys-
talline state, same as initial quinone monoimines VIIIa–
In order to make a correct comparison of the processes
of hydrochlorination and hydrobromination of quinone
monoimines Xa–Xf the hydrochlorination of these qui-
none monoimines was carried out under the treatment
with HCl in aqueous AcOH. The reaction products were
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

AVDEENKO et al.
218
Scheme 4.
Hlg
OH
Me
NH
Me
NH
OH
Hlg
C
O
X
X
C
O
Me
NH
Me
[O]
HHlg
XVIIa–XVf,
XVIIIa–XVIIIf
XVa–XVf, XVIa–XVIf
OH
N
O
C
O
X
X
C
O
Br
Me
Xa–Xf
IXa–IXf
OH
AcNH
Br
XIX
X = Me (a), 4-MeOC6H4 (b), 4-MeC6H4 (c), C6H5 (d), 4-ClC6H4 (e), 4-NO2C6H4 (f); Hlg = Cl (XV, XVII), Br (XVI, XVIII).
1
analyzed by H NMR without preliminary purification.
The isomer ratio remained the same within the error
limits of the experiment as at the hydrochlorination with
gaseous HCl in chloroform, therefore the nature of the
solvent did not considerably affect the course of the
hydrochlorination.
structures G and H. The analysis of the charge distribution
in the protonated form obtained by the quantum-chemical
calculations shows that structure G is more favorable,
and in this structure the charge on the atom C6 is more
positive [+0.010 (X = Me), –0.058 (X = Ph)] than on the
atom C2 [–0.815 (X = Me), –0.360 (X = Ph)].
The different isomer ratio in the products of the
hydrochlorination and hydrobromination of the N-acyl-
(aroyl)-3-methyl-1,4-benzoquinonemonoimines may be
attributed to two routes of hydrohalogenation.
The subsequent addition of the chloride anion may
take two directions, into positions 2 or 6 of the ring, since
the energy of the transition states I and J is materially the
same, the energy difference equals only 1.4 (X = Me) and
4.2 kJ mol−1 (X = Ph). The addition of the chloride anion
into the position 5 is unfavorable by energy: The energy
of this structure exceeds the energy of the transition state
I by 215.1 (X = Me), 177.1 kJ mol−1 (X = Ph).
The hydrochlorination of quinone monoimines Xa–Xf
starts with the protonation of the initial reagents, same
as with quinone monoimines IIa–IIf unsubstituted in the
quinoid ring (Scheme 5, route a). The transition state that
forms in this event may be presented as two boundary
Since the energy of the transition states I and J is
materially the same and in the protonated form atom C6
is more positive, the addition of the chloride anion occurs
both to the position 2 giving aminophenols XVII and to
the position 6 forming aminophenols XV, and the latter
direction prevails (Scheme 5). Namely, the hydrochlori-
nation of the N-acetyl(aroyl)-3-methyl-1,4-benzoquinone
monoimines proceeds along the ionic mechanism with
the charge control.
Composition of products of hydrohalogenation of
N-acetyl(aroyl)-3-methyl-1,4-benzoquinone monoimines
Xa–Xf
Content of isomers, %
hydrochlorination
products
hydrobromination
products
Quinone
imine
XV
70
80
73
75
77
70
XVII
30
XVI
–
XVIII
–
The hydrohalogenation of quinone monoimines Xa–
Xf was carried out at room temperature in air. As already
mentioned, HCl is not oxidized by the air oxygen and
difficultly forms radical species, and HBr under these
conditions readily forms radical species [21]. N-Aroyl-
1,4-benzoquinone monoimines possess the highest re-
dox potentials among all known quinone monoimines
[26], therefore they considerably easier are reduced
Xa
Xb
Xc
Xd
Xe
Xf
20
90
65
74
59
48
10
27
35
25
26
23
41
30
52
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
219
Scheme 5.
Me
2
N
O
e_, H+
X
6
5
H+
H
O
a
X
b
Me
Me
Me
Me
.
+
H
H
H
N
O
N
N
O
O
N
O
H
X
X
X
.
X
+
O
O
O
O
K
H
G
_
L
_
.
_
Hlg
.
+Hlg
Hlg
+Hlg
Hlg
Hlg
OH
Me
Me
Me
Me
H
H
H
H
N
N
OH
Hlg
N
O
N
O
X
X
X
X
O
O
H
O
O
J
Hlg
XVII, XVIII
XV, XVI
I
X = Me, Ph; Hlg = Cl, Br.
and form anion-radical species. In the series of quinone
monoimines Xb–Xc–Xd–Xe–Xf with decreasing donor
and increasing acceptor properties of the substituent in
the para-position of the aryl fragment the redox potential
of quinone monoimines Xb–Xf should grow [27], and
this should result in the easier formation of anion-radical
species.According to the experimental data, in this series
grows the content of isomer XVIII (Scheme 5, route b)
formed in the hydrobromination. Yet in the case of the
hydrochlorination the content of the corresponding isomer
XVII changes insignificantly.
The experimental data and the quantum-chemical
calculations lead to the conclusion that the hydrobromi-
nation of quinone monoimines Xa–Xf occurs along two
parallel routes, along the ionic and the radical mechanisms
(Scheme 5, routes a and b).
In event of the ionic mechanism, like in the hydro-
chlorination in the first stage the protonation occurs of the
initial quinone monoimine at the nitrogen atom, and then
the addition of the bromide anion. Also positions 2 and 6
of the ring are favorable by the energy: The energy of the
transition states I and J is virtually the same, the energy
difference equals only 0.13 (X = Me), 2.15 kJ mol−1
(X = Ph). The energy of the transition state with the ad-
dition of the bromide anion into the position 5 exceeds
the energy of the transition state I by 189.24 (X = Me),
129.4 kJ mol−1 (X = Ph). Thus if the hydrobromination
proceeded only by the ionic mechanism in all cases like
in the hydrochlorination the main product should be
aminophenol XVI in contrast to the experimental data.
As already stated, since HBr is prone to the formation
of radical species the contribution of the radical mecha-
nism to the hydrobromination becomes significant.At the
radical mechanism in the first stage occurs one-electron
transfer and the protonation at the nitrogen atom provid-
ing a radical species of the initial quinone monoimine
with the boundary structures K and L (Scheme 5, route
b).According to the calculations structure K is preferable,
therewith the density of the localization of the partially
free LUMO is larger on the atom C2 [0.228 (X = Me),
0.347 (X = Ph)], than on the atom C6 [0.140 (X = Me),
0.260 (X = Ph)]. Consequently, the subsequent addition
of the radical species Br• occurs predominantly into the
position 2 with the orbital control: The partially free
LUMO of the radical species of the quinone monoimine
interacts with the partially occupied HOMO of the
radical bromine species. As a result forms the transition
structure J that in its turn transforms into aminophenol
XVIII.
The most stable representatives of N-acetyl-
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AVDEENKO et al.
220
Scheme 6.
R1
R1
R1
R1
[O]
[O]
HHlg
O
AcN
AcNH
OH
AcNH
OH
O
AcN
R2
R2
R2
XXIa–XXIc
R2
XXa–XXc
Hlg
Hlg
XXIIa–XXIIc, XXIIIa–XXIIIc
XXIVa–XXIVc, XXVa–XXVc
R1 = R2 = Me (a), R1 = Pr-i, R2 = Me (b), R1 = Me, R2 = Pr-i (c); Hlg = Cl (XXII, XXIV), Br (XXIII, XXV).
(aroyl)-1,4-benzoquinone monoimines are the quinone
monoimines with two alkyl substituents in the quinoid
ring. In the hydrohalogenation of 2,5-dialkyl-N-aroyl-1,4-
benzoquinone monoimines only products of 1,4-addition
were found [28], the hydrohalogenation of 2,5-dialkyl-N-
acetyl-1,4-benzoquinone monoimines was not previously
studied.
the doublet from the atom H5 in the region δ 6.52 and
6.58 ppm. In the spectra of quinone monoimines XXIVc,
XXVc quartets are observed from the atom H3 (δ 6.66 and
6.64 ppm), doublets of the hydrogen atoms of the 2-Me
group (δ 2.05 and 2.07 ppm), and a singlet of protons from
the group MeCO (δ 2.31 ppm). The character of these
spectra unambiguously confirms the assumed structure
of quinone monoimines XXIVa–XXIVc, XXVa–XXVc.
2,5-Dialkyl-N-acetyl-1,4-benzoquinone monoimines
XXIa–XXIc were obtained by oxidation of the
corresponding aminophenols XXa–XXc with silver oxide
in chloroform (Scheme 6).
Thus our research permitted the establishment of
the fact that the hydrohalogenation of N-acetyl(aroyl)-
1,4-benzoquinone monoimines independent of the
substituents in the quinoid ring occurred exclusively as
1,4-addition. The hydrochlorination proceeds by the ionic
mechanism, whereas the hydrobromination, both by ionic
and radical mechanism.
The hydrochlorination of 2,5-dialkyl-N-acetyl-1,4-
benzoquinone monoimines XXIa–XXIc was performed
with gaseous hydrogen chloride in chloroform, the
hydrobromination was carried out in acetic acid by
adding equimolar quantity of the 40% hydrobromic acid.
The reaction products were analyzed by NMR without
preliminary purification.
EXPERIMENTAL
IR spectra of compounds synthesized were recorded
on a spectrophotometer UR-20 from pellets with KBr or
solutions in chloroform. 1H and 13C NMR spectra were
registered on a spectrometer Varian VXR-300 at operating
frequencies 300 (1H) and 75.4 MHz (13C) with respect
to TMS. TLC was carried out on Silufol UV-254 plates.
Chloroform was used as solvent, eluent benzene–hexane,
1:10, development under UV irradiation.
In all cases only products of 1,4-addition were obtained,
2,5-dialkyl-4-amino-N-acetyl-6-halophenols XXIIa–
XXIIc, XXIIIa–XXIIIc. Notwithstanding the presence
of the bulky isopropyl group the hydrohalogenation of
quinine monoimine XXIc proceeded just at the C=C
bond containing this group. In order to more exact
establishment of the structure of the obtained compounds
they were oxidized with silver(I) oxide in chloroform
into the corresponding imines XXIVa–XXIVc, XXVa–
XXVc for the spectra of the oxidized forms were more
informative.
Quantum-chemical calculations were performed
with the use of Firefly QC software[29] that is partially
underlain by the initial code of GAMESS (US) package
[30]. The search for the transition states was carried out
along the standard procedure of the structure optimization.
1
In the H NMR spectra of quinone monoimines
XXIVa, XXVa quartets appear from the atom H3 (δ
6.71 and 6.69 ppm), doublets from the protons of the
2-Me group (δ 2.08 and 2.09 ppm), and two singlets of
protons of groups 5-Me and MeCO. The characteristic
feature of the 1H NMR spectra of quinone monoimines
XXIVb, XXVb is the presence of singlet signals from
hydrogen atoms of the groups 3-Me and MeCO and of
4-Amino-N-acetyl(aroyl)phenols Ia–If, 4-amino-N-
acetyl(aroyl)-2-chlorophenols IIIa–IIIf, 4-amino-N-
acetyl(aroyl)-3-chlorophenols IVa–IVf, and 4-amino-
N-aroyl-2(3)-methylphenols VIIa–VIIf, IXa–IXf were
obtained by procedure [31], 4-amino-N-acetyl-2,5-
dimethylphenol (XXa), 4-amino-N-acetyl-6-isopropyl-
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HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
221
3-methylphenol (XXb), 4-amino-N-acetyl-5-isopropyl-
s (1H, NH). Found, %: C 53.29, 53.41; H 3.12, 3.60;
2-methyl-phenol (XXc), by method [32].
Cl 12.17, 12.48; N 9.34, 9.50. C13H9ClN2O4. Calculated,
%: C 53.35; H 3.10; Cl 12.11; N 9.57.
The characteristics of aminophenols Ia–If are in
agreement with the published data: Ia, mp 168–169°C
(169°C [33]); Ib, mp 223–225°C (226–230°C [34, 35]);
Ic, mp 214–216°C (190°C [36]); Id, mp 212–214°C
(221°C [36]); Ie, mp 255–256°C (250°C [37]); If, mp
271–272°C (258°C [38]); IVb, mp 199–200°C (200–
201°C [35]); VIIa, mp 181–183°C (179–180°C [39]);
IXa, mp 125–127°C (129–130°C [35, 39]); IXb, mp
216–218°C (223–225°C [35]).
4-Amino-2-methyl-N-(4-methoxybenzoyl)phenol
(VIIb). Yield 83%, mp 192–194°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.12 s (3H, 2-Me), 3.83 s (3H,
MeO), 6.74 d (1H, H6, J 8.7 Hz), 7.33–7.36 d.d (1H, H5,
J 9.0 Hz), 7.42 q (1H, H3, J 1.2 Hz), 7.04–7.94 d.d (4H,
4-MeOC6H4, J 8.7 Hz), 9.18 s (1H, OH), 9.80 s (1H, NH).
Found, %: C 70.11, 70.34; H 5.86, 6.22; N 5.42, 5.79.
C15H15NO3. Calculated, %: C 70.02; H 5.88; N 5.44.
4-Amino-N-acetyl-3-chlorophenol (IVa). Yield 35%,
mp 123–124°C. 1H NMR spectrum (DMSO-d6), δ, ppm:
2.01 s (3H, Me), 6.69–6.72 d.d (1H, H6, J 2.4 Hz), 6.84 d
(1H, H2, J2,6 1.5 Hz), 7.29 d (1H, H5, J5,6 8.4 Hz), 9.32 s
(1H, OH), 9.78 s (1H, NH). Found, %: C 51.75, 51.93;
H 4.28, 4.40; Cl 18.99, 19.16; N 7.54, 7.90. C8H8ClNO2.
Calculated, %: C 51.77; H 4.34; Cl 19.10; N 7.55.
4-Amino-2-methyl-N-(4-methylbenzoyl)phenol
(VIIc). Yield 86%, mp 228.5–230°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.16 s (3H, 2-Me), 2.42 s (3H,
Me), 6.70 d (1H, H6, J 8.7 Hz), 7.31–7.35 d.d (1H, H5,
J 8.7 Hz), 7.41 q (1H, H3, J 1.5 Hz), 7.04–7.96 d.d (4H,
4-MeC6H4, J 9.0 Hz), 8.81 s (1H, OH), 9.65 s (1H, NH).
Found, %: C 74.55, 74.82; H 6.31, 6.49; N 5.80, 6.16.
C15H15NO2. Calculated, %: C 74.67; H 6.27; N 5.81.
4-Amino-N-(4-methylbenzoyl)-3-chlorophenol
(IVc). Yield 48%, mp 213–214.5°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.38 s (3H, Me), 6.76–6.79 d.d
(1H, H6, J 2.1 Hz), 6.92 q (1H, H2, J 2.7 Hz), 7.28 d
(1H, H5, J5,6 7.8 Hz), 7.04–7.96 d.d (4H, 4-MeC6H4,
J 7.8 Hz), 9.77 s (1H, OH), 9.89 s (1H, NH). Found, %:
C 64.23, 64.57; H 4.31, 4.68; Cl 13.49, 13.70; N 5.29,
5.62. C14H12ClNO2. Calculated, %: C 64.25; H 4.62;
Cl 13.55; N 5.35.
4-Amino-N-benzoyl-2-methylphenol (VIId). Yield
82%, mp 203–204°C. 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.13 s (3H, 2-Me), 6.74 d (1H, H6, J 8.4 Hz), 7.35–
7.38 d.d (1H, H5, J 9.0 Hz), 7.44 q (1H, H3, J 1.2 Hz),
7.48–7.94 m (5H, Ph), 9.16 s (1H, OH), 9.96 s (1H, NH).
Found, %: C 73.92, 74.35; H 5.68, 5.91; N 6.18, 6.44.
C14H13NO2. Calculated, %: C 73.99; H 5.77; N 6.16.
4-Amino-2-methyl-N-(4-bromobenzoyl)phenol
(VIIe). Yield 81%, mp 208.5–210°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.14 s (3H, 2-Me), 6.71 d (1H, H6,
J 9.0 Hz), 7.29–7.33 d.d (1H, H5, J 8.7 Hz), 7.39 q (1H,
H3, J 1.2 Hz), 7.64–7.91 d.d (4H, 4-BrC6H4, J 9.0 Hz),
8.88 s (1H, OH), 9.82 s (1H, NH). Found, %: C 54.67,
54.82; H 3.90, 4.21; N 4.67, 4.88. C14H12BrNO2. Calcu-
lated, %: C 54.92; H 3.95; N 4.58.
4-Amino-N-benzoyl-3-chlorophenol (IVd). Yield
1
44%, mp 195–197°C. H NMR spectrum (DMSO-d6),
δ, ppm: 6.77–6.81 d.d (1H, H6, J 2.1 Hz), 6.93 q (1H,
H2, J 2.4 Hz), 7.31 d (1H, H5, J5,6 9.0 Hz), 7.49–7.99 m
(5H, Ph), 9.86 s (1H, OH), 9.91 s (1H, NH). Found, %:
C 63.07, 63.51; H 4.09, 4.28; Cl 14.16, 14.37; N 5.62,
5.80. C13H10ClNO2. Calculated, %: C 63.04; H 4.07;
Cl 14.31; N 5.66.
4-Amino-2-methyl-N-(4-nitrobenzoyl)phenol
(VIIf). Yield 78%, mp 262–263.5°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.13 s (3H, 2-Me), 6.76 d (1H, H6,
J 8.7 Hz), 7.36–7.39 d.d (1H, H5, J 9.0 Hz), 7.45 q (1H,
H3, J 1.5 Hz), 8.16–8.35 d.d (4H, 4-NO2C6H4, J 9.0 Hz),
9.22 s (1H, OH), 10.27 s (1H, NH). Found, %: C 61.80,
62.05; H 4.39, 4.57; N 10.18, 10.43. C14H12N2O4. Cal-
culated, %: C 61.76; H 4.44; N 10.29.
4-Amino-N-(4-chlorobenzoyl)-3-chlorophenol
1
(IVe). Yield 52%, mp 204–205°C. H NMR spectrum
(DMSO-d6), δ, ppm: 6.77–6.80 d.d (1H, H6, J 2.4 Hz),
6.93 q (1H, H2, J 2.4 Hz), 7.29 d (1H, H5, J 9.0 Hz),
7.60–7.99 d.d (4H, 4-ClC6H4, J 8.4 Hz), 9.94 s (1H, OH),
9.98 s (1H, NH). Found, %: C 55.47, 55.68; H 3.20, 3.49;
Cl 25.07, 25.19; N 4.68, 4.90. C13H9Cl2NO2. Calculated,
%: C 55.34; H 3.22; Cl 25.13; N 4.96.
4-Amino-3-methyl-N-(4-methylbenzoyl)phenol
(IXc). Yield 75%, mp 208–210°C. Found, %: C 74.58,
74.90; H 6.23, 6.51; N 5.53, 5.89. C15H15NO2. Calculated,
%: C 74.67; H 6.27; N 5.81.
4-Amino-N-(4-nitrobenzoyl)-3-chlorophenol (IVf).
Yield 44%, mp 224–226°C. 1H NMR spectrum (DMSO-
d6), δ, ppm: 6.78–6.82 d.d (1H, H6, J 2.1 Hz), 6.94 q (1H,
H2, J 2.4 Hz), 7.32 d (1H, H5, J5,6 8.7 Hz), 8.19–8.38 d.d
(4H, 4-NO2C6H4, J 9.0 Hz), 9.98 s (1H, OH), 10.25
4-Amino-N-benzoyl-3-methylphenol (IXг). Yield
89%, mp 202–204°C. Found, %: C 74.03, 74.29; H 5.68,
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AVDEENKO et al.
222
5.91; N 6.14, 6.32. C14H13NO2. Calculated, %: C 73.99;
H 5.77; N 6.16.
hexane.
N-(4-Bromobenzoyl)-2-methyl-1,4-benzoquinone
monoimine (VIIIe). Yield 79%, mp 118–120°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.04 d (3H, 2-Me, J 1.2 Hz),
6.66 d (1H, H6, J 9.9 Hz), 6.85 q (1H, H3, J 1.2 Hz),
7.02–7.06 d.d (1H, H5, J 9.9 Hz), 7.63–7.80 d.d (4H,
4-BrC6H4, J 8.7 Hz). Found, %: C 55.14, 55.38; H 3.27,
3.50; N 4.61, 4.89. C14H10BrNO2. CычandCлeHO, %:
C 55.29; H 3.31; N 4.61.
4-Amino-3-methyl-N-(4-chlorobenzoyl)phenol
(IXe). Yield 85%, mp 203–204°C. Found, %: C 64.09,
64.28; H 4.53, 4.79; N 5.38, 5.61. C14H12ClNO2. Calcu-
lated, %: C 64.25; H 4.62; N 5.35.
4-Amino-3-methyl-N-(4-nitrobenzoyl)phenol (IXf).
Yield 68%, mp 236–238°C. Found, %: C 61.66, 61.90;
H 4.28, 4.53; N 10.27, 10.54. C14H12N2O4. Calculated,
%: C 61.76; H 4.44; N 10.29.
2-Methyl-N-(4-nitrobenzoyl)-1,4-benzoquinone
monoimine (VIIIf). Yield 79%, mp 118–120°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.06 d (3H, 2-Me, J 1.5 Hz),
6.70 d (1H, H6, J 9.9 Hz), 6.87 q (1H, H3, J 1.2 Hz),
7.05–7.08 d.d (1H, H5, J 9.6 Hz), 8.12–8.34 d.d (4H,
4-BrC6H4, J 9.0 Hz). Found, %: C 62.08, 62.34; H 3.55,
3.89; N 10.17, 10.40. C14H10N2O4. Calculated, %:
C 62.22; H 3.73; N 10.37.
N-Acetyl-4-amino-2,5-dimethylphenol (XXa). Yield
30%, mp 174–176°C. Found, %: C 67.10, 67.32; H 7.14,
7.50; N 7.62, 7.89. C10H13NO2. Calculated, %: C 67.02;
H 7.31; N 7.82.
4-Amino-N-acetyl-6-isopropyl-3-methylphenol
(XXb). Yield 43%, mp 177–178°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.12 d (6H, 6-CHMe2, J 6.6 Hz),
1.97 s (3H, 3-Me), 2.02 s (3H, MeCO), 3.07–3.17 m
(1H, 6-CHMe2), 6.58 s (1H, H5), 6.92 s (1H, H2), 9.04 s
(1H, NH), 9.06 s (1H, OH). Found, %: C 69.44, 69.71;
H 8.28, 8.53; N 6.70, 6.22. C12H17NO2. Calculated, %:
C 69.54; H 8.27; N 6.76.
N-Acetyl-3-methyl-1,4-benzoquinone monoimine
1
(Xa). Yield 61%, mp 118–120°C. H NMR spectrum
(CDCl3), δ, ppm: 2.16 d (3H, 3-Me, J 1.5 Hz), 2.31 s
(3H, MeCO), 6.50–6.51 d.d (1H, H6, J 1.2 Hz), 6.54 q
(1H, H2, J 1.5 Hz), 6.86 d (1H, H5, J 9.0 Hz). Found, %:
C 66.08, 66.34; H 5.55, 5.89; N 8.17, 8.40. C9H9NO2.
Calculated, %: C 66.25; H 5.56; N 8.58.
4-Amino-N-acetyl-5-isopropyl-2-methylphenol
(XXc). Yield 37%, mp 180°C. Found, %: C 69.54, 69.83;
H 8.12, 8.57; N 6.70, 6.94. C12H17NO2. Calculated, %:
C 69.54; H 8.27; N 6.76.
3-Methyl-N-(4-methoxybenzoyl)-1,4-benzoquinone
monoimine (Xb). Yield 83%, mp 104–106°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.29 d (3H, 3-Me, J 1.2 Hz),
3.88 s (3H, MeO), 6.45–6.48 d.d (1H, H6, J 9.9 Hz),
6.60 q (1H, H2, J 1.5 Hz), 6.87 d (1H, H5, J5,6 9.6 Hz),
6.96–7.84 d.d (4H, 4-MeOC6H4, J 8.7 Hz). 13C NMR
spectrum (CDCl3), δ, ppm: 17.6 (3-Me), 55.5 (OMe),
114.0 (C3', C5'), 124.5 (C1'), 131.2 (C5), 131.6 (C2', C6'),
132.5 (C2), 134.0 (C6), 148.0 (C3), 157.1 (C4), 164.2
(C4'), 179.3 (C=O), 186.6 (C1). Found, %: C 70.42, 70.61;
H 5.09, 5.37; N 5.33, 5.68. C15H13NO3. Calculated, %:
C 70.58; H 5.13; N 5.49.
N-Acetyl(aroyl)-1,4-benzoquinone monoimines
IIa–IIf, VIIIa–VIIIf, Xa–Xf, XXIa–XXIc. a. Into 10 ml
of dry chloroform was added 0.01 mol of the correspond-
ing 4-amino-N-acetyl(aroyl)phenol, and at stirring was
added 0.012 mol of silver(I) oxide. The dispersion was
heated to 40°C at vigorous stirring over 30 min, the solu-
tion turned yellow. The silver precipitate was filtered off
from the reaction mixture, the solvent was distilled off in
a vacuum. The formed precipitate of the quinone imine
was recrystallized from the mixture benzene–hexane.
N-Acetyl(aroyl)-1,4-benzoquinone monoimines IIa–IIf,
VIIIa–VIIId were not isolated from the reaction solution
obtained by removing the silver precipitate. The reaction
solution was purified by column chromatography, the
solvent was evaporated, the quinone imine obtained as
uncrystallizable oily substance was dissolved in an ap-
propriate solvent (chloroform or acetic acid) and was used
for further hydrohalogenation.
3-Methyl-N-(4-methylbenzoyl)-1,4-benzoquinone
1
monoimine (Xc). Yield 81%, mp 88–89°C. H NMR
spectrum (CDCl3), δ, ppm: 2.30 d (3H, 3-Me, J 1.5 Hz),
2.44 s (3H, 4-MeC6H4), 6.44–6.48 d.d (1H, H6,
J 10.2 Hz), 6.61 q (1H, H2, J 2.1 Hz), 6.85 d (1H, H5,
J5,6 10.2 Hz), 7.28–7.78 d.d (4H, 4-MeC6H4, J 8.4 Hz).
13C NMR spectrum (CDCl3), δ, ppm: 17.6 (3-Me), 21.7
(MeC6H4), 129.3 (C1'), 129.4 (C3', C5'), 129.5 (C2', C6'),
131.1 (C5), 132.5 (C2), 134.1 (C6), 145.0 (C4'), 147.8
(C3), 157.0 (C4), 179.7 (C=O), 186.5 (C1). Found, %:
C 74.92, 75.30; H 5.61, 5.84; N 5.80, 6.19. C15H13NO2.
Calculated, %: C 75.30; H 5.48; N 5.85.
b. N-Acetyl(aroyl)-1,4-benzoquinone monoimines
were obtained by the oxidation of appropriate aminophe-
nols with lead tetraacetate in acetic acid [31] and were
recrystallized from acetic acid or the mixture benzene–
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HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
223
N-Benzoyl-3-methyl-1,4-benzoquinone monoimine
(Xd). 1H NMR spectrum (CDCl3), δ, ppm: 2.31 d (3H,
3-Me, J 1.5 Hz), 6.46–6.49 d.d (1H, H6, J 9.0 Hz),
6.61 q (1H, H2, J 1.2 Hz), 6.87 d (1H, H5, J5,6 10.2 Hz),
7.48–7.90 m (5H, Ph).
H 7.42, 7.61; N 6.99, 7.36. C12H15NO2. Calculated, %:
C 70.22; H 7.37; N 6.82.
Hydrochlorination of N-acetyl(aroyl)-1,4-
benzoquinone monoimines IIa–IIf, VIIIa–VIIIf,
Xa–Xf, XXIa–XXIc. Through a solution of 0.01 mol
of quinone monoimine IIa–IIf, VIIIa–VIIIf, Xa–Xf,
XXIa–XXIc in 5 ml of dry chloroform a flow of dry
gaseous hydrogen chloride was passed over 20 min,
the reaction solution got lighter, a colorless precipitate
separated that was filtered off and analyzed by 1H NMR
without additional purification. In order to characterize
pure compounds and for their further use in oxidation
the precipitate was subjected to recrystallization from
benzene.
3-Methyl-N-(4-chlorobenzoyl)-1,4-benzoquinone
monoimine (Xe). Yield 83%, mp 102–104°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.29 d (3H, 3-Me, J 1.2 Hz),
6.47–6.51 d.d (1H, H6, J 10.6 Hz), 6.62 q (1H, H2,
J 1.5 Hz), 6.86 d (1H, H5, J5,6 10.2 Hz), 7.48–7.85 d.d
(4H, 4-ClC6H4, J 8.7 Hz). 13C NMR spectrum (CDCl3),
δ, ppm: 17.7 (3-Me), 129.2 (C3', C5'), 130.4 (C1'), 130.7
(C2', C6'), 131.0 (C5), 132.8 (C2), 134.4 (C6), 140.5 (C4'),
147.6 (C3), 157.7 (C4), 178.7 (C=O), 186.4 (C1). Found,
%: C 64.51, 64.78; H 3.82, 3.99; Cl 13.40, 13.65; N 5.18,
5.42. C14H10ClNO2. Calculated, %: C 64.75; H 3.88;
Cl 13.65; N 5.39.
4-Amino-N-acetyl-2-chlorophenol (IIIa). Yield
1
47%, mp 140–141°C. H NMR spectrum (DMSO-d6),
δ, ppm: 1.99 s (3H, Me), 6.89 d (1H, H6, J5,6 8.7 Hz),
7.20–7.23 d.d (1H, H5, J3,5 1.2 Hz), 7.68 d (1H, H3,
J 2.7 Hz), 9.82 s (1H, OH), 9.85 s (1H, NH). Found, %:
C 51.63, 51.84; H 4.32, 4.60; Cl 19.11, 19.45; N 7.69,
7.92. C8H8ClNO2. Calculated, %: C 51.77; H 4.34;
Cl 19.10; N 7.55.
3-Methyl-N-(4-nitrobenzoyl)-1,4-benzoquinone
monoimine (Xf). Yield 92%, mp 172–173°C. 1H NMR
spectrum (CDCl3), δ, ppm: 2.32 d (3H, 3-Me, J 0.9 Hz),
6.52–6.55 d.d (1H, H6, J 9.0 Hz), 6.65 q (1H, H2,
J 1.2 Hz), 6.89 d (1H, H5, J5,6 10.2 Hz), 8.10–8.35 d.d
(4H, 4-NO2C6H4, J 2.4 Hz). 13C NMR spectrum (CDCl3),
δ, ppm: 17.7 (3-Me), 124.0 (C3', C5'), 130.5 (C2', C6'),
130.8(C5), 133.2 (C2), 134.9 (C6), 137.1 (C1'), 147.4
(C3), 150.8 (C4'), 158.6 (C4), 177.6 (C=O), 186.3 (C1).
Found, %: C 62.21, 62.45; H 3.68, 3.91; N 10.44, 10.68.
C14H10N2O4. Calculated, %: C 62.22; H 3.73; N 10.37.
4-Amino-N-(4-methoxybenzoyl)-2-chlorophenol
1
(IIIb). Yield 78%, mp 228–229°C. H NMR spectrum
(DMSO-d6), δ, ppm: 3.84 s (3H, MeO), 6.95 d (1H, H6,
J5,6 8.7 Hz), 7.03–7.96 d.d (4H, 4-MeOC6H4, J 9.0 Hz),
7.48–7.51 d.d (1H, H5, J3,5 2.1 Hz), 7.83 d (1H, H3,
J 2.4 Hz), 9.94 br.s (1H, OH), 9.99 br.s (1H, NH).
13C NMR spectrum, δ, ppm: 55.4 (OMe), 113.6 (C3',
C5'), 116.4 (C6), 119.1 (C2), 120.6 (C5), 122.1 (C3), 126.9
(C1'), 129.6 (C2', C6'), 131.9 (C4), 149.3 (C1), 161.9 (C4'),
164.7 (C=O). Found, %: C 60.21, 60.49; H 4.42, 4.75;
Cl 12.62, 12.94; N 5.10, 5.48. C14H12ClNO3. Calculated,
%: C 60.55; H 4.36; Cl 12.77; N 5.04.
N-Acetyl-2,5-dimethyl-1,4-benzoquinone monoi-
1
mine (XXIa). Yield 65%, mp 64–65°C. H NMR
spectrum (CDCl3), δ, ppm: 2.00 d (3H, 2-Me, J 1.2 Hz),
2.13 d (3H, 5-Me, J 1.5 Hz), 2.31 s (3H, MeCO), 6.53 q
(1H, H3, J 1.2 Hz), 6.66 q (1H, H5, J 1.5 Hz). Found, %:
C 67.43, 67.70; H 6.09, 6.35; N 7.98, 8.22. C10H11NO2.
Calculated, %: C 67.78; H 6.26; N 7.90.
4-Amino-N-(4-methylbenzoyl)-2-chlorophenol
1
N-Acetyl-6-isopropyl-3-methyl-1,4-benzoquinone
monoimine (XXIb). Yield 80%, mp 26–27°C. 1H NMR
spectrum (CDCl3), δ, ppm: 1.10 d (6H, 6-CHMe2,
J 5.7 Hz), 2.13 br.s (3H, 3-Me), 2.32 br.s (3H, MeCO),
3.01–3.09 m (1H, 6-CHMe2), 6.51 s (1H, H2), 6.54 s (1H,
H5). Found, %: C 70.09, 70.25; H 7.34, 7.62; N 6.89, 7.16.
C12H15NO2. Calculated, %: C 70.22; H 7.37; N 6.82.
(IIIc). Yield 76%, mp 217–218°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.38 s (3H, Me), 6.95 d (1H, H6,
J 8.7 Hz), 7.31–7.87 d.d (4H, 4-MeC6H4, J 8.1 Hz), 7.48–
7.52 d.d (1H, H5, J5,6 9.0 Hz), 7.84 d (1H, H3, J3,5 2.7 Hz),
9.97 s (1H, OH), 10.07 s (1H, NH). 13C NMR spectrum,
δ, ppm: 21.0 (MeC6H4), 116.4 (C6), 119.0 (C2), 120.5
(C5), 122.0 (C3), 127.6 (C3', C5'), 128.9 (C2', C6'), 131.7
(C4), 132.0 (C1'), 141.5 (C4'), 149.3 (C1), 165.0 (C=O).
Found, %: C 64.38, 6.51; H 4.07, 4.39; Cl 13.50, 13.72;
N 5.31, 5.66. C14H12ClNO2. Calculated, %: C 64.25;
H 4.62; Cl 13.55; N 5.35.
N-Acetyl-5-isopropyl-2-methyl-1,4-benzoquinone
monoimine (XXIc). Yield 95%, mp 72–73°C. 1H NMR
spectrum (CDCl3), δ, ppm: 1.19 d (6H, 5-CHMe2,
J 7.2 Hz), 2.01 d (3H, 2-Me, J 1.5 Hz), 2.31 s (3H,
MeCO), 3.14–3.23 m (1H, 5-CHMe2), 6.49 br.s (1H,
H6), 6.67 q (1H, H3, J 1.2 Hz). Found, %: C 70.04, 70.35;
4-Amino-N-benzoyl-2-chlorophenol (IIId). Yield
1
72%, mp 177–178°C. H NMR spectrum (DMSO-d6),
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δ, ppm: 6.95 d (1H, H6, J 9.0 Hz), 7.48–7.52 d.d (1H,
H5, J5,6 8.7 Hz), 7.49–7.94 m (5H, Ph), 7.85 d (1H, H3,
J3,5 2.4 Hz), 9.95 s (1H, OH), 10.14 s (1H, NH). 13C NMR
spectrum, δ, ppm: 116.4 (C6), 119.1 (C2), 120.6 (C5),
122.0 (C3), 127.6 (C3', C5'), 128.4 (C2', C6'), 131.5 (C4'),
131.6 (C1'), 134.9 (C4), 149.4 (C1), 165.2 (C=O). Found,
%: C 62.85, 63.04; H 4.15, 4.37; Cl 14.30, 14.58; N 5.69,
5.81. C13H10ClNO2. Calculated, %: C 63.04; H 4.07;
Cl 14.31; N 5.66.
2-Me), 2.38 s (3H, 4-MeC6H4), 7.32–7.85 d.d (4H,
4-MeC6H4, J 8.1 Hz), 7.43 d (1H, H3, J 2.1 Hz), 7.71 d
(1H, H5, J 2.4 Hz), 8.33 s (1H, NH), 10.03 s (1H, OH).
13C NMR spectrum, δ, ppm: 17.1 (2-Me), 21.0 (MeC6H4),
119.2 (C3), 120.2 (C6), 121.8 (C5), 126.9 (C2), 127.6 (C3',
C5'), 128.9 (C2', C6'), 131.7 (C4), 132.0 (C1'), 141.5 (C4'),
147.0 (C1), 165.0 (C=O). Found, %: C 65.58, 65.71;
H 5.08, 5.49; Cl 12.94, 13.34; N 5.12, 5.60. C15H14ClNO2.
Calculated, %: C 65.34; H 5.12; Cl 12.86; N 5.08.
4-Amino-N-(4-chlorobenzoyl)-2-chlorophenol
4-Amino-N-benzoyl-2-methyl-6-chlorophenol
1
(IIIe). Yield 59%, mp 190–191°C. H NMR spectrum
1
(XId). Yield 87%, mp 184–186°C. H NMR spectrum
(DMSO-d6), δ, ppm: 6.96 d (1H, H6, J 9.0 Hz), 7.30–
7.97 d.d (4H, 4-ClC6H4, J 8.7 Hz), 7.48–7.52 d.d (1H,
H5, J5,6 9.0 Hz), 7.84 d (1H, H3, J3,5 2.4 Hz), 10.10 s
(1H, OH), 10.24 s (1H, NH). Found, %: C 55.33, 55.61;
H 3.20, 3.48; Cl 25.17, 25.39; N 4.95, 5.18. C13H9Cl2NO2.
Calculated, %: C 55.34; H 3.22; Cl 25.13; N 4.96.
(DMSO-d6), δ, ppm: 2.21 s (3H, 2-Me), 7.43 d (1H, H3,
J 2.4 Hz), 7.49–7.94 m (5H, Ph), 7.72 d (1H, H5, J 2.7 Hz),
8.96 br.s (1H, NH), 10.11 s (1H, OH). 13C NMR spectrum,
δ, ppm: 17.1 (2-Me), 119.2 (C3), 120.2 (C6), 121.8 (C5),
127.0 (C2), 127.6 (C3', C5'), 128.4 (C2', C6'), 131.5 (C4'),
131.6 (C4), 135.0 (C1'), 147.1 (C1), 165.3 (C=O). Found,
%: C 64.08, 64.32; H 4.65, 4.79; Cl 13.50, 13.82; N 5.30,
5.66. C14H12ClNO2. Calculated, %: C 64.25; H 4.62;
Cl 13.55; N 5.35.
4-Amino-N-(4-nitrobenzoyl)-2-chlorophenol
1
(IIIf). Yield 42%, mp 244–246°C. H NMR spectrum
(DMSO-d6), δ, ppm: 6.96 d (1H, H6, J 8.4 Hz), 7.50–
7.53 d.d (1H, H5, J5,6 9.0 Hz), 7.86 d (1H, H3, J3,5 2.7 Hz),
8.17–8.37 d.d (4H, 4-NO2C6H4, J 9.0 Hz), 10.08 s (1H,
OH), 10.47 s (1H, NH). Found, %: C 53.40, 53.71;
H 3.02, 3.48; Cl 12.16, 12.57; N 9.62, 9.85. C13H9ClN2O4.
Calculated, %: C 53.35; H 3.10; Cl 12.11; N 9.57.
4-Amino-N-(4-bromobenzoyl)-2-methyl-6-
chlorophenol (XIf). Yield 84%, mp 160–162oC. 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.21 s (3H, 2-Me),
7.42 d (1H, H3, J 1.8 Hz), 7.70 d (1H, H5, J 2.4 Hz),
7.74–7.90 d.d (4H, 4-BrC6H4, J 8.4 Hz), 8.32 s (1H, NH),
10.18 s (1H, OH). Found, %: C 49.58, 49.72; H 3.22,
3.61; Cl 10.35, 10.76; N 4.08, 4.29. C14H11BrClNO2.
Calculated, %: C 49.37; H 3.26; Cl 10.41; N 4.11.
4-Amino-N-acetyl-2-methyl-6-chlorophenol
1
(XIa). Yield 69%, mp 98–100°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.00 s (3H, 2-Me), 2.17 s (3H,
MeCO), 7.17 q (1H, H3, J 2.1 Hz), 7.57 q (1H, H5,
J 2.1 Hz), 8.34 s (1H, NH), 9.91 s (1H, OH). Found, %:
C 53.48, 53.79; H 4.88, 5.12; Cl 17.35, 17.66; N 7.09,
7.34. C9H10ClNO2. Calculated, %: C 54.15; H 5.05;
Cl 17.76; N 7.02.
4-Amino-2-methyl-N-(4-nitrobenzoyl)-6-
chlorophenol (XIf). Yield 51%, mp 256–258°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.22 s (3H,
2-Me), 7.42 d (1H, H3, J 2.1 Hz), 7.72 d (1H, H5,
J 2.4 Hz), 8.16–8.37 d.d (4H, 4-NO2C6H4, J 9.0 Hz),
9.07 s (1H, NH), 10.43 s (1H, OH). 13C NMR spectrum,
δ, ppm: 17.1 (2-Me), 119.3 (C3), 120.2 (C6), 121.9 (C5),
123.5 (C3', C5'), 127.1 (C2), 129.1 (C2', C6'), 131.1 (C4),
140.4 (C1'), 147.5 (C1), 149.1 (C4'), 163.4 (C=O). Found,
%: C 54.52, 54.73; H 3.58, 3.91; Cl 11.49, 11.62; N 9.06,
9.37. C14H11ClN2O4. Calculated, %: C 54.83; H 3.62;
Cl 11.56; N 9.13.
4-Amino-2-methyl-N-(4-methoxybenzoyl)-6-
chlorophenol (XIb). Yield 92%, mp 166–168°C.
1H NMR spectrum NMR spectrum (DMSO-d6), δ, ppm:
2.21 s (3H, 2-Me), 3.84 s (3H, MeO), 7.05–7.94 d.d (4H,
4-MeOC6H4, J 9.0 Hz), 7.43 d (1H, H3, J 2.1 Hz), 7.72 d
(1H, H5, J 2.4 Hz), 8.33 s (1H, NH), 9.97 s (1H, OH).
13C NMR spectrum, δ, ppm: 17.1 (2-Me), 55.4 (OMe),
113.6 (C3', C5'), 119.1 (C5), 120.1 (C6), 121.8 (C3), 126.8
(C1'), 126.9 (C2), 129.5 (C2', C6'), 131.8 (C4), 146.9 (C1),
161.9 (C4'), 164.6 (C=O). Found, %: C 61.48, 61.59;
H 4.80, 4.92; Cl 12.35, 12.67; N 4.88, 5.03. C15H14ClNO3.
Calculated, %: C 61.76; H 4.84; Cl 12.15; N 4.80.
4-Amino-N-acetyl-3-methyl-6-chlorophenol (XVa).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.01 s (3H,
3-Me), 2.08 s (3H, MeO), 6.81 s (1H, H2), 7.28 s (1H,
H5), 8.34 s (1H, NH), 9.25 s (1H, OH).
4-Amino-3-methyl-N-(4-methoxybenzoyl)-6-
chlorophenol (XVb). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.12 s (3H, 3-Me), 3.83 s (3H, MeO), 6.86 s (1H,
H2), 7.03–7.92 d.d (4H, 4-MeOC6H4, J 8.7 Hz), 7.25 s
4-Amino-2-methyl-N-(4-methylbenzoyl)-6-
chlorophenol (XIc). Yield 69%, mp 156–158°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.21 s (3H,
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225
(1H, H5), 9.62 s (1H, NH), 10.06 s (1H, OH).
4-Amino-3-methyl-N-(4-nitrobenzoyl)-2-
chlorophenol (XVIIf). 1H NMR spectrum (DMSO-d6),
δ, ppm: 2.21 s (3H, 3-Me), 6.86 d (1H, H6, J 6.7 Hz),
7.09 d (1H, H5, J 9.0 Hz), 8.18–8.37 d.d (4H, 4-NO2C6H4,
J 8.7 Hz), 10.12 s (1H, NH), 10.32 s (1H, OH).
4-Amino-3-methyl-N-(4-methylbenzoyl)-6-
1
chlorophenol (XVc). H NMR spectrum (DMSO-d6),
δ, ppm: 2.12 s (3H, 3-Me), 2.38 s (3H, Me), 6.85 s (1H,
H2), 7.26 s (1H, H5), 7.32–7.86 d.d (4H, 4-MeC6H4,
J 7.8 Hz), 9.68 s (1H, NH), 10.04 s (1H, OH).
4-Amino-N-acetyl-2,5-dimethyl-6-chlorophenol
(XXIIa). Yield 70%, mp 213–215°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.12 s (3H, 2-Me), 2.14 s (3H,
5-Me), 2.41 s (3H, MeCO), 6.92 s (1H, H3), 8.88 br.s
(1H, NH), 9.32 c (1H, OH). Found, %: C 56.15, 56.43;
H 5.62, 5.81; Cl 16.66, 16.98; N 6.58, 6.74. C10H12ClNO2.
Calculated, %: C 56.21; H 5.66; Cl 16.59; N 6.56.
4-Amino-N-benzoyl-3-methyl-6-chlorophenol
1
(XVd). H NMR spectrum (DMSO-d6), δ, ppm: 2.13 s
(3H, 3-Me), 6.88 s (1H, H2), 7.27 s (1H, H5), 7.49–7.97 m
(5H, Ph), 9.78 s (1H, NH), 10.08 s (1H, OH).
4-Amino-3-methyl-6-chloro-N-(4-chlorobenzoyl)-
phenol (XVe). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.13 s (3H, 3-Me), 6.87 s (1H, H2), 7.28 s (1H, H5),
7.60–7.98 d.d (4H, 4-ClC6H4, J 8.7 Hz), 9.86 s (1H, NH),
10.08 s (1H, OH).
4-Amino-N-acetyl-6-isopropyl-3-methyl-2-
chlorophenol (XXIIb). Yield 75%, mp 196°C. 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.14 d (6H, 6-CHMe2,
J 7.0 Hz), 1.99 s (3H, 3-Me), 2.11 s (3H, MeCO),
3.18–3.28 m (1H, 6-CHMe2), 6.93 s (1H, H5), 8.86 br.s
(1H, NH), 9.39 s (1H, OH). Found, %: C 56.39, 56.66;
H 6.14, 6.39; Cl 14.58, 14.72; N 5.66, 5.83. C12H16ClNO2.
Calculated, %: C 59.63; H 6.67; Cl 14.67; N 5.79.
4-Amino-3-methyl-N-(4-nitrobenzoyl)-6-
1
chlorophenol (XVf). H NMR spectrum (DMSO-d6),
δ, ppm: 2.15 s (3H, 3-Me), 6.88 s (1H, H2), 7.32 s (1H,
H5), 8.18–8.37 d.d (4H, 4-NO2C6H4, J 8.4 Hz), 10.11 s
(1H, NH), 10.26 br.s (1H, OH).
4-Amino-N-acetyl-5-isopropyl-2-methyl-6-
chlorophenol (XXIIc). Yield 91%, mp 195–197°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.27 d (6H,
5-CHMe2, J 6.9 Hz), 1.98 s (3H, 2-Me), 2.13 s (3H,
MeCO), 3.26–3.37 m (1H, 5-CHMe2), 6.77 s (1H,
H3), 8.87 br.s (1H, NH), 9.22 s (1H, OH). Found, %:
C 59.70, 59.99; H 6.54, 6.82; Cl 14.66, 14.80; N 5.28,
5.53. C12H16ClNO2. Calculated, %: C 59.63; H 6.67;
Cl 14.67; N 5.79.
4-Amino-N-acetyl-3-methyl-2-chlorophenol
(XVIIa). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.01 s
(3H, 3-Me), 2.15 s (3H, MeO), 6.81 d (1H, H6, J 7.8 Hz),
6.98 d (1H, H5, J 8.4 Hz), 9.14 br.s (1H, NH), 9.41 br.s
(1H, OH).
4-Amino-3-methyl-N-(4-methoxybenzoyl)-2-
chlorophenol (XVIIb). 1H NMR spectrum (DMSO-d6),
δ, ppm: 2.18 s (3H, 3-Me), 3.83 s (3H, MeO), 6.83 d
(1H, H6, J 9.0 Hz), 7.03–7.92 d.d (4H, 4-MeOC6H4,
J 8.7 Hz), 7.04 d (1H, H5, J 8.1 Hz), 9.78 s (1H, NH),
10.06 s (1H, OH).
N-Acetyl-2-methyl(2,5-dialkyl)-6-chloro-1,4-ben-
zoquinone monoimines XIIIb–XIIIf, XXIVa–XXIVc.
Into 10 ml of dry chloroform was added 0.01 mol of the
corresponding N-acetylphenol XIb–XIf, XXIIa–XXIIc,
and at stirring was added 0.012 mol of silver(I) oxide. The
dispersion was heated to 40°C at vigorous stirring over
30 min, the solution turned yellow. The silver precipitate
was filtered off from the reaction mixture, the solvent was
distilled off in a vacuum. The residue was recrystallized
from the mixture benzene–hexane.
4-Amino-3-methyl-N-(4-methylbenzoyl)-2-
chlorophenol (XVIIc). 1H NMR spectrum (DMSO-d6),
δ, ppm: 2.18 s (3H, 3-Me), 2.38 s (3H, Me), 6.83 d (1H,
H6, J 6.6 Hz), 7.04 d (1H, H5, J 8.4 Hz), 7.32–7.86 d.d
(4H, 4-MeC6H4, J 7.8 Hz), 9.84 s (1H, NH), 10.06 s
(1H, OH).
4-Amino-N-benzoyl-3-methyl-2-chlorophenol
(XVIId). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.19 s
(3H, 3-Me), 6.85 d (1H, H6, J 6.6 Hz), 7.05 d (1H, H5,
J 8.4 Hz), 7.49–7.97 m (5H, Ph), 9.94 s (1H, NH), 10.11 s
(1H, OH).
2-Methyl-N-(4-methoxybenzoyl)-6-chloro-1,4-
benzoquinone monoimine (XIIIb). Yield 69%, mp
124–126°C. 1H NMR spectrum (CDCl3), δ, ppm: 2.10 d
(3H, 2-Me, J 1.8 Hz), 3.89 s (3H, MeO), 6.90 q (1H, H3,
J 1.5 Hz), 6.97–7.87 d.d (4H, 4-MeOC6H4, J 9.3 Hz),
7.25 d (1H, H5, J 2.7 Hz). Found, %: C 62.13, 62.47;
H 4.18, 4.59; Cl 12.39, 12.70; N 4.68, 4.95. C15H12ClNO3.
Calculated, %: C 62.19; H 4.17; Cl 12.24; N 4.83.
4-Amino-3-methyl-2-chloro-N-(4-chlorobenzoyl)-
phenol (XVIIe). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.19 s (3H, 3-Me), 6.85 d (1H, H6, J 6.0 Hz), 7.05 d (1H,
H5, J 9.0 Hz), 7.60–7.98 d.d (4H, 4-ClC6H4, J 8.7 Hz),
10.01 s (1H, NH), 10.09 s (1H, OH).
2-Methyl-N-(4-methylbenzoyl)-6-chloro-1,4-
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80–82°C. 1H NMR spectrum (CDCl3), δ, ppm: 1.37 d (6H,
5-CHMe2, J 7.2 Hz), 2.05 d (3H, 2-Me, J 1.2 Hz), 2.31 s
(3H, MeCO), 3.60–3.70 m (1H, 5-CHMe2), 6.66 q (1H,
H3, J 1.2 Hz). Found, %: C 60.11, 60.42; H 5.83, 6.01;
Cl 14.57, 15.85; N 5.79, 5.98. C12H14ClNO2. Calculated,
%: C 60.13; H 5.89; Cl 14.79; N 5.84.
benzoquinone monoimine (XIIIc). Yield 63%, mp
110–112°C. 1H NMR spectrum (CDCl3), δ, ppm: 2.09 d
(3H, 2-Me, J 1.2 Hz), 2.44 c (3H, MeO), 6.89 q (1H,
H3, J 1.5 Hz), 7.24 d (1H, H5, J 2.7 Hz), 7.29–7.79 d.d
(4H, 4-MeC6H4, J 8.7 Hz). Found, %: C 65.72, 66.09;
H 4.38, 4.51; Cl 12.92, 13.40; N 5.06, 5.27. C15H12ClNO2.
Calculated, %: C 65.82; H 4.42; Cl 12.95; N 5.12.
Hydrobromination of N-acetyl(aroyl)-1,4-ben-
zoquinone monoimines VIIIa–VIIIf, Xa–Xf, XXIa–
XXIc. Into a solution of 0.01 mol of quinone monoimine
in 10 ml of AcOH was added by portions while stirring
2 ml of 40% HBr. The reaction mixture got lighter. On
adding water a colorless precipitate formed. The obtained
mixtures without further purification were analyzed by
1H NMR. In order to characterize pure compounds and for
their further use in oxidation the precipitate was subjected
to recrystallization from AcOH.
N-Benzoyl-2-methyl-6-chloro-1,4-benzoquinone
monoimine (XIIId). Yield 76%, mp 112–114°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.10 d (3H, 2-Me,
J 1.5 Hz), 6.90 q (1H, H3, J 1.5 Hz), 7.25 d (1H, H5,
J 2.4 Hz), 7.42–7.92 m (5H, Ph). Found, %: C 64.52,
64.87; H 3.58, 3.91; Cl 13.79, 13.88; N 5.06, 5.47.
C14H10ClNO2. Calculated, %: C 64.75; H 3.88; Cl 13.65;
N 5.39.
N-(4-Bromobenzoyl)-2-methyl-6-chloro-1,4-
benzoquinone monoimine (XIIIe). Yield 63%, mp 122–
124°C. 1H NMR spectrum (CDCl3), δ, ppm: 2.12 d (3H,
2-Me, J 1.5 Hz), 6.89 q (1H, H3, J 1.2 Hz), 7.25 d (1H,
H5, J 2.1 Hz), 7.64–7.79 d.d (4H, 4-BrC6H4, J 9.0 Hz).
Found, %: C 49.52, 49.81; H 2.57, 2.96; Cl 10.49, 10.75;
N 4.06, 4.33. C14H9BrClNO2. Calculated, %: C 49.66;
H 2.68; Cl 10.47; N 4.14.
4-Amino-6-bromo-2-methyl-N-(4-methoxybenzoyl)
1
phenol (XIIb). Yield 80%, mp 252°C. H NMR
spectrum NMR spectrum (DMSO-d6), δ, ppm: 2.23 s
(3H, 2-Me), 3.84 s (3H, MeO), 7.05–7.94 d.d (4H,
4-MeOC6H4, J 9.0 Hz), 7.47 d (1H, H3, J 2.1 Hz), 7.85 d
(1H, H5, J 2.7 Hz), 9.79 br.s (1H, NH), 9.94 br.s (1H, OH).
Found, %: C 53.49, 53.70; H 4.08, 4.29; Br 23.75, 24.18;
N 4.07, 4.59. C15H14BrNO3. Calculated, %: C 53.59;
H 4.20; Br 23.77; N 4.17.
2-Methyl-N-(4-nitrobenzoyl)-6-chloro-1,4-
benzoquinone monoimine (XIIIf). Yield 80%, mp
139–141°C. 1H NMR spectrum (CDCl3), δ, ppm: 2.14 d
(3H, 2-Me, J 1.5 Hz), 6.92 q (1H, H3, J 1.5 Hz), 7.27 d
(1H, H5, J 3.0 Hz), 8.13–8.34 d.d (4H, 4-NO2C6H4,
J 9.3 Hz). Found, %: C 54.82, 55.17; H 2.58, 2.96;
Cl 11.49, 11.70; N 9.06, 9.33. C14H9ClN2O4. Calculated,
%: C 55.19; H 2.98; Cl 11.64; N 9.19.
4-Amino-6-bromo-2-methyl-N-(4-methylbenzoyl)
phenol (XIIc). Yield 79%, subl. temp. 244°C. 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.23 s (3H, 2-Me), 2.38 s
(3H, Me), 7.32–7.86 d.d (4H, 4-MeC6H4, J 8.1 Hz), 7.48 d
(1H, H3, J 2.1 Hz), 7.83 d (1H, H5, J 3.9 Hz), 9.86 br.s (1H,
NH), 10.01 s (1H, OH). Found, %: C 56.38, 56.70; H 4.22,
4.42; Br 24.65, 24.89; N 4.18, 4.39. C15H14BrNO2.
Calculated, %: C 56.27; H 4.41; Br 24.96; N 4.37.
N-Acetyl-2,5-dimethyl-6-chloro-1,4-benzoquinone
monoimine (XXIVa). Yield 63%, mp 122–124°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.08 d (3H, 2-Me,
J 1.5 Hz), 2.30 s (3H, 5-Me), 2.32 s (3H, MeCO), 6.71 q
(1H, H3, J 1.2 Hz). Found, %: C 56.43, 56.77; H 4.80,
5.06; Cl 16.29, 16.49; N 6.40, 6.91. C10H10ClNO2.
Calculated, %: C 56.75; H 4.76; Cl 16.75; N 6.62.
4-Amino-N-benzoyl-6-bromo-2-methylphenol
(XIId). Yield 65%, subl. temp. 210°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 2.24 s (3H, 2-Me), 7.48 d (1H,
H3, J 2.1 Hz), 7.52–7.95 m (5H, Ph), 7.86 d (1H, H5,
J 2.7 Hz), 9.82 br.s (1H, NH), 10.09 br.s (1H, OH). Found,
%: C 54.58, 54.71; H 3.22, 3.60; Br 26.11, 26.49; N 4.08,
4.37. C14H12BrNO2. Calculated, %: C 54.92; H 3.95;
Br 26.10; N 4.58.
N-Acetyl-6-isopropyl-3-methyl-2-chloro-1,4-
benzoquinone monoimine (XXIVb). Yield 89%, mp
1
48–50°C. H NMR spectrum (CDCl3), δ, ppm: 1.21 d
(6H, 6-CHMe2, J 7.2 Hz), 2.17 s (3H, 3-Me), 2.23 s
(3H, MeCO), 3.21–3.30 m (1H, 6-CHMe2), 6.52 d (1H,
H5, J 1.2 Hz). Found, %: C 59.84, 60.12; H 5.75, 5.93;
Cl 14.80, 15.21; N 5.73, 5.92. C12H14ClNO2. Calculated,
%: C 60.13; H 5.89; Cl 14.79; N 5.84.
4-Amino-6-bromo-2-methyl-N-(4-bromobenzoyl)
phenol (XIIe). Yield 65%, mp 178–180°C. H NMR
1
spectrum (DMSO-d6), δ, ppm: 2.23 s (3H, 2-Me),
7.47 d (1H, H3, J 1.8 Hz), 7.74–7.89 d.d (4H, 4-CrC6H4,
J 8.1 Hz), 7.85 d (1H, H5, J 2.7 Hz), 10.02 br.s (1H, NH),
10.17 br.s (1H,OH). Found, %: C 43.58, 43.76; H 2.23,
2.59; Br 41.05, 41.27; N 3.80, 3.99. C14H11Br2NO2.
N-Acetyl-5-isopropyl-2-methyl-6-chloro-1,4-
benzoquinone monoimine (XXIVc). Yield 77%, mp
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HYDROHALOGENATION OF N-ACETYL(AROYL)-1,4-BENZOQUINONE MONOIMINES
227
(3H, 3-Me), 6.84 d (1H, H6, J 9.0 Hz), 7.09 d (1H, H5,
J 9.0 Hz), 7.49–7.97 m (5H, Ph), 9.90 br.s (1H, NH),
10.01 br.s (1H, OH).
Calculated, %: C 43.67; H 2.88; Br 41.50; N 3.64.
4-Amino-6-bromo-2-methyl-N-(4-nitrobenzoyl)
1
phenol (XIIf). Yield 67%, mp 204–206°C. H NMR
spectrum (DMSO-d6), δ, ppm: 2.24 s (3H, 2-Me), 7.48 d
(1H, H3, J 2.1 Hz), 7.86 s (1H, H5, J 2.4 Hz), 8.19–
8.37 d.d (4H, 4-NO2C6H4, J 8.4 Hz), 10.29 br.s (1H, NH),
10.42 br.s (1H, OH). Found, %: C 47.55, 47.63; H 3.22,
3.58; Br 22.61, 22.97; N 7.68, 7.90. C14H11BrN2O4.
Calculated, %: C 47.89; H 3.16; Br 22.75; N 7.98.
4-Amino-2-bromo-3-methyl-N-(4-chlorobenzoyl)
phenol (XVIIIe). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.23 s (3H, 3-Me), 6.83 d (1H, H6, J 8.1 Hz), 7.07 d (1H,
H5, J 8.1 Hz), 7.59–7.96 d.d (4H, 4-ClC6H4, J 8.7 Hz),
10.01 br.s (1H, NH), 10.19 br.s (1H, OH).
4-Amino-2-bromo-3-methyl-N-(4-nitrobenzoyl)
phenol (XVIIIf). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.26 s (3H, 3-Me), 6.87 d (1H, H6, J 8.4 Hz), 7.13 d (1H,
H5, J 8.4 Hz), 8.19–8.36 d.d (4H, 4-NO2C6H4, J 9.0 Hz),
9.86 br.s (1H, NH), 10.27 br.s (1H, OH).
4-Amino-6-bromo-3-methyl-N-(4-methoxybenzoyl)
phenol (XVIb). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.11 s (3H, 3-Me), 3.83 s (3H, MeO), 6.85 s (1H, H2),
7.02–7.90 d.d (4H, 4-MeOC6H4, J 9.0 Hz), 7.39 s (1H,
H5), 9.77 br.s (1H, NH), 10.05 br.s (1H, OH).
4-Amino-N-acetyl-2,6-dibromo-3-methylphenol
1
4-Amino-6-bromo-3-methyl-N-(4-methylbenzoyl)
phenol (XVIc). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.11 s (3H, 3-Me), 2.38 s (3H, Me), 6.85 s (1H, H2),
7.32–7.86 d.d (4H, 4-MeC6H4, J 8.7 Hz), 7.39 s (1H, H5),
9.67 br.s (1H, NH), 9.96 br.s (1H, OH).
(XIX). Yield 31%, mp 243–245°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.02 s (3H, 3-Me), 2.19 s (3H,
MeCO), 7.46 s (1H, H5), 9.50 s (1H, NH), 9.71 br.s (1H,
OH). Found, %: C 33.17, 33.48; H 2.59, 2.70; Br 49.32,
49.56; N 4.37, 4.60. C9H9Br2NO2. Calculated, %:
C 33.47; H 2.81; Br 49.48; N 4.34.
4-Amino-N-benzoyl-6-bromo-3-methylphenol
(XVId). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.13 s
(3H, 3-Me), 6.86 s (1H, H2), 7.41 s (1H, H5), 7.49–7.97 m
(5H, Ph), 9.73 br.s (1H, NH), 10.05 br.s (1H, OH).
4-Amino-N-acetyl-6-bromo-2,5-dimethylphenol
(XXIIIa). Yield 84%, mp 230–232°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.99 s (3H, 2-Me), 2.16 s (3H, 5-Me),
2.17 s (3H, MeCO), 6.94 s (1H, H3), 8.81 s (1H, NH),
9.32 br.s (1H, OH). Found, %: C 46.47, 46.78; H 4.59,
4.82; Br 40.31, 40.55; N 5.39, 5.60. C10H12BrNO2.
Calculated, %: C 46.53; H 4.69; Br 30.96; N 5.43.
4-Amino-6-bromo-3-methyl-N-(4-chlorobenzoyl)
phenol (XVIe). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.11 s (3H, 3-Me), 6.85 s (1H, H2), 7.40 s (1H, H5),
7.59–7.96 d.d (4H, 4-ClC6H4, J 8.7 Hz), 9.85 br.s (1H,
NH), 10.14 br.s (1H, OH).
4-Amino-N-acetyl-2-bromo-6-isopropyl-3-methyl-
1
phenol (XXIIIb). Yield 69%, mp 182°C. H NMR
4-Amino-6-bromo-3-methyl-N-(4-nitrobenzoyl)
phenol (XVIf). 1H NMR spectrum (DMSO-d6), δ, ppm:
2.14 s (3H, 3-Me), 6.88 s (1H, H2), 7.45 s (1H, H5),
8.19–8.36 d.d (4H, 4-NO2C6H4, J 9.0 Hz), 10.10 br.s (1H,
NH), 10.38 br.s (1H, OH).
spectrum (DMSO-d6), δ, ppm: 1.13 d (6H, 6-CHMe2,
J 6.9 Hz), 1.99 s (3H, 3-Me), 2.15 s (3H, MeCO),
3.20–3.29 m (1H, 6-CHMe2), 6.96 s (1H, H5), 8.86 br.s
(1H, NH), 9.39 br.s (1H, OH). Found, %: C 50.29, 50.48;
H 5.61, 5.83; Br 27.60, 27.91; N 4.70, 4.93. C12H16BrNO2.
Calculated, %: C 50.37; H 5.64; Br 27.92; N 4.89.
4-Amino-2-bromo-3-methyl-N-(4-methoxybenzoyl)
1
phenol (XVIIIb). H NMR spectrum (DMSO-d6), δ,
ppm: 2.23 s (3H, 3-Me), 3.83 s (3H, MeO), 6.83 d (1H,
H6, J 8.7 Hz), 7.02–7.90 d.d (4H, 4-MeOC6H4, J 8.7 Hz),
7.04 d (1H, H5, J 8.7 Hz), 9.61 br.s (1H, NH), 9.89 s
(1H, OH).
4-Amino-N-acetyl-6-bromo-5-isopropyl-2-
methylphenol (XXIIIc). Yield 56%, mp 168–169°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.25 d (6H,
5-CHMe2, J 6.9 Hz), 1.98 s (3H, 2-Me), 2.15 s (3H,
MeCO), 3.43–3.48 m (1H, 5-CHMe2), 6.79 s (1H,
H3), 8.81 s (1H, NH), 9.19 br.s (1H, OH). Found, %:
C 50.41, 50.56; H 5.34, 5.62; Br 27.81, 27.99; N 4.66,
4.90. C12H16BrNO2. Calculated, %: C 50.37; H 5.64;
Br 27.92; N 4.89.
4-Amino-2-bromo-3-methyl-N-(4-methylbenzoyl)
1
phenol (XVIIIc). H NMR spectrum (DMSO-d6), δ,
ppm: 2.23 s (3H, 3-Me), 2.38 s (3H, Me), 6.83 d (1H,
H6, J 8.7 Hz), 7.07 d (1H, H5, J 8.7 Hz), 7.32–7.86 d.d
(4H, 4-MeC6H4, J 7.5 Hz), 9.84 br.s (1H, NH), 9.96 br.s
(1H, OH).
N-Aroyl-6-bromo-2-methyl-1,4-benzoquinone
monoimines XIVe, XIVf and N-acetyl-6-bromo-2,5-
dialkyl-1,4-benzoquinone monoimines XXVa–XXVc.
4-Amino-N-benzoyl-2-bromo-3-methylphenol
(XVIIId). 1H NMR spectrum (DMSO-d6), δ, ppm: 2.24 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 2 2011

AVDEENKO et al.
228
Into 10 ml of dry chloroform was added 0.01 mol of
the corresponding N-acetyl(aroyl)phenol XIIe, XIIf,
XXIIIa–XXIIIc and at stirring was added 0.012 mol
of silver(I) oxide. The dispersion was heated to 40°C at
vigorous stirring over 30 min, the solution turned yellow.
The silver precipitate was filtered off from the reaction
mixture, the solvent was distilled off in a vacuum. The
residue was recrystallized from the mixture benzene–
hexane.
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1
monoimine (XXVa). Yield 92%, mp 127°C. H NMR
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