Halogenation of N-substituted p-quinone monoimines and p-quinone monooxime esrers: XI. Synthesis and halogenation of 4-[aryl(alkyl)aminocarbonyl-oxyimino] cyclohexa-2,5-dien-1-ones

Article abstract of DOI:10.1134/S1070428010060102

4-[Aryl(alkyl)aminocarbonyloxyimino]cyclohexa-2,5-dien-1-ones were synthesized by treatment of various substituted p-quinone monooximes with aryl isocyanates. The selectivity in the halogenation of the obtained p-quinone monooxime esters depended on the s

Full text of DOI:10.1134/S1070428010060102

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 6, pp. 830–843. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, A.G. Sergeeva, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 6,
pp. 837–849.
Halogenation of N-Substituted p-Quinone Monoimines
and p-Quinone Monooxime Esrers: XI.* Synthesis
and Halogenation of 4-[Aryl(alkyl)aminocarbonyl-
oxyimino]cyclohexa-2,5-dien-1-ones
A. P. Avdeenko, S. A. Konovalova, and A. G. Sergeeva
Donbass State Machine Building Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
Received August 24, 2009
Abstract—4-[Aryl(alkyl)aminocarbonyloxyimino]cyclohexa-2,5-dien-1-ones were synthesized by treatment of
various substituted p-quinone monooximes with aryl isocyanates. The selectivity in the halogenation of the
obtained p-quinone monooxime esters depended on the substrate structure and was either completely (syn
addition) or partly regioselective (syn or anti addition). In all cases, the effect of steric factor was crucial, and
the reaction was accompanied by halogenation of the aryl fragment.
DOI: 10.1134/S1070428010060102
We previously synthesized N-alkyl(aryl)aminocar-
bonyl-1,4-benzoquinone monoimines by reaction of
alkyl and aryl isocyanates with various aminophenols
and subsequent oxidation [2]. N-Alkyl(aryl)aminocar-
bonyl-3,5-dimethyl-1,4-benzoquinone monoimines
reacted with alcohols to give 1-aryl-4,7a-dimethyl-
7,7a-dihydro-1H-benzimidazole-2,6-diones [3] due to
the presence of NH group in the initial quinone imine.
Isocyanates are capable of reacting with both amines
and alcohols [4]; therefore, reactions of aryl isocy-
anates with p-quinone monooximes were expected to
afford compounds belonging to a new class of para-
quinone monooxime esters, 4-(arylaminocarbonyloxy-
imino)cyclohexa-2,5-dien-1-ones. O-Arylsulfonyl
[5, 6] and O-aroyl [6, 7] para-quinone monooximes
were synthesized previously. It was found that the
direction of their halogenation is determined by elec-
tronic (difference in the polarities of the quinoid C=C
bonds) and steric factors (size and position of substit-
uents in the quinoid ring). Here, the effect of substit-
uent on the oxime oxygen atom on the reactivity ratio
of the quinoid C=C bonds in O-aroyl derivatives was
stronger than in their O-arylsulfonyl analogs [8].
2,5-dien-1-ones; the difference is that an NH group is
present between the aryl fragment and carbonyl group
in the former. A similar difference in the structures of
N-aroyl- and N-alkyl(aryl)aminocarbonyl-3,5-di-
methyl-1,4-benzoquinone monoimines gave rise to
considerable difference in their reactivity [3].
The goal of the present work was to synthesize new
4-[aryl(alkyl)aminocarbonyloxyimino]cyclohexa-2,5-
dien-1-ones and study their reactions with halogens.
4-[Aryl(alkyl)aminocarbonyloxyimino]cyclohexa-2,5-
dien-1-ones IIIa–IIIab were obtained by reaction of
p-quinone monooximes Ia–Ik with aryl and alkyl iso-
cyanates IIa–IId on heating in dioxane (Scheme 1).
The structure of compounds IIIa–IIIab was confirmed
by the 1H NMR and IR spectra and elemental analyses.
We also did not rule out the possibility for aryl (alkyl)
isocyanates to react with another tautomeric form of
p-quinone monooximes, the corresponding p-nitroso-
1
phenols. However, the H NMR and IR data showed
the absence of isocyanate addition products at the hy-
droxy group of p-nitrosophenol.
It was found previously that 4-(aroyloxyimino)-
cyclohexa-2,5-dien-1-ones are characterized by
a higher energy barrier to Z–E isomerization about the
C=N bond (ΔG≠ > 100 kJ/mol) [9], as compared to
the corresponding p-quinone monoimines (ΔG≠ = 44–
4-(Arylaminocarbonyloxyimino)cyclohexa-2,5-di-
en-1-ones are analogs of 4-(aroyloxyimino)cyclohexa-
* For communication X, see [1].
830

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
831
Scheme 1.
O
O
R1
R2
R4
R3
R1
R2
R4
N
+
X
·
R3
O
N
N
C(O)NHX
OH
O
Ia–Ik
IIa–IId
IIIa–IIIab
I, R1 = R2 = R3 = R4 = H (a); R1 = Me, R2 = R3 = R4 = H (b); R1 = R3 = R4 = H, R2 = Me (c); R1 = R2 = H, R3 = R4 = Me (d); R1 =
R3 = Me, R2 = R4 = H (e); R1 = i-Pr, R2 = R4 = H, R3 = Me (f); R1 = Me, R2 = R4 = H, R3 = i-Pr (g); R1 = R4 = H, R2 = R3 = Me (h);
R1 = R4 = Me, R2 = R3 = H (i); R1 = R4 = i-Pr, R2 = R3 = H (j); R1 = R4 = t-Bu, R2 = R3 = H (k); II, X = Ph (a), 4-MeC6H4 (b), Bu (c),
t-Bu (d); III, R1 = R2 = R3 = R4 = H (a, b); R1 = Me, R2 = R3 = R4 = H (c, d); R1 = R3 = R4 = H, R2 = Me (e, f); R1 = R2 = H, R3 = R4 =
Me (g, h, i); R1 = R3 = Me, R2 = R4 = H (j, k, l, aa); R1 = i-Pr, R2 = R4 = H, R3 = Me (m, n); R1 = Me, R2 = R4 = H, R3 = i-Pr (o, p);
R1 = R4 = H, R2 = R3 = Me (q–s); R1 = R4 = Me, R2 = R3 = H (t–v, ab); R1 = R4 = i-Pr, R2 = R3 = H (w, x); R1 = R4 = t-Bu, R2 =
R3 = H (y, z); X = Ph (a, c, e, g, j, m, o, q, t, w, y), 4-MeC6H4 (b, d, f, h, k, n, p, r, u, x, z), 3-ClC6H4 (i, l, s, v), Bu (aa), t-Bu (ab).
46 kJ/mol) [10]. Therefore, their Z–E isomerization
becomes improbable, and particular isomers of unsym-
metrically substituted p-quinone monooxime esters can
be isolated as individual substances. It was also shown
that halogenation of these compounds is not accom-
panied by Z–E isomerization [8]. According to the
1H NMR data, 4-arylaminocarbonyloxyimino-2-meth-
ylcyclohexa-2,5-dien-1-ones IIIc and IIId isolated by
recrystallization exist in solution as mixtures of Z and
E isomers at a ratio of 60 : 40 (IIIc) or 15 : 85 (IIId).
The observed difference in the Z/E isomer ratios is
explained by the fact that the Z and E isomers of
4-tolyl derivative IIId are separated more readily by
recrystallization. The ratio of the Z and E isomers of
both phenyl derivative IIIc and 4-tolyl derivative IIId
in the crude product (before recrystallization) was
~60:40. While studying halogenation of 4-(arylsul-
fonyloxyimino)cyclohexa-2,5-dien-1-ones we suc-
ceeded in isolating individual E isomer only for the
4-tolyl derivative [8].
4-(Arylaminocarbonyloxyimino)cyclohexa-2,5-di-
en-1-ones IIIa–IIIz were subjected to chlorination
with gaseous chlorine which was passed until complete
saturation of the reaction mixture. The bromination of
these compounds was carried out using molecular
bromine in acetic acid or chloroform, the substrate-to-
bromine ratio being 1:5. Crystalline products isolated
1
as a result of halogenation were analyzed H NMR
spectroscopy before recrystallization with a view to
reveal all possible isomers. Many compounds were
isolated as individual substances by recrystallization,
so that we were able to determine the composition of
almost all product mixtures. The results are shown in
Scheme 2.
Halogenation of p-quinone monooxime esters IIIa
and IIIb having no substituents in the quinoid ring led
to the formation of several isomers. The chlorination
of IIIa and IIIb gave products of addition of one
halogen molecule at the double C=C bond in the
quinoid ring (compounds IVa and IVd), as well as
2,5,6-trichlorocyclohex-2-en-1-ones IVb and IVe, the
latter being formed via successive halogenation–dehy-
drohalogenation. Among bromination products, we
detected only 2,5,6-tribromocyclohex-2-en-1-ones IVc
and IVf having a bromine atom at the quinoid C=C
bond. Obviously, compounds IVc and IVf were
formed via addition of bromine molecule to p-quinone
monooxime esters resulting from successive bromina-
tion–dehydrobromination. Analysis of the composition
of the reaction mixtures showed that the addition of
first halogen molecule to p-quinone monooxime esters
IIIa and IIIb is regioselective: it involves preferen-
tially the quinoid C=C bond located syn with respect to
the oxime fragment (the ratio of the syn- and anti-
addition products is 57 : 43 in the chlorination and
p-Quinone monooximes Ia–Ik reacted with alkyl
isocyanates IIc and IId under relatively severe condi-
tions, and the yield of 4-alkylaminocarbonyloxyimino-
cyclohexa-2,5-dien-1-ones was poor even on pro-
longed heating in dioxane at 100°C; the conversion of
the initial p-quinone monooxime was incomplete, and
a number of by-products were formed. We succeeded
in isolating only two individual 4-alkylaminocarbonyl-
oxyiminocyclohexa-2,5-dien-1-ones IIIaa and IIIab
(yield 8 and 15%, respectively); therefore, the reac-
tivity of these compounds toward halogens was not
studied. The poor yields of IIIaa and IIIab are likely
to result from lower reactivity of aliphatic isocyanates
compared to aryl isocyanates toward compounds
having a hydroxy group.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
832
Scheme 2.
R6
R1
R7
R8
O
Hlg
Hlg
R5
R4
O
R2
O
N
R3
N
H
E Isomers: IVa–IVf, Va–Vd, VIa–VId, VIIa–VIIi
VIIIa–VIIIi, IXa–IXc, XIa–XIf, XIIa–XIIg
O
N
R6
O
R1
R1
R2
R4
R7
R8
R5
R2
R4
Hlg2
O
R3
Hlg
N
C(O)NHX
Hlg
R3
N
O
H
O
IIIa–IIIz
Z Isomers: IVa–IVf, Va–Vd, Xa–Xd, XIIa–XIIc
R6
R7
O
R1
R5
R2
O
R4
R8
N
R3
N
O
H
XIIIa, XIIIb, XIV, XV, XVIa–XVIg, XVII, XVIIIa–XVIIId
IV, R2 = R3 = R6 = R8 = H: R1 = R4 = H, Hlg = R5 = R7 = Cl (a); R1 = H, Hlg = R4 = R5 = R7 = Cl (b); R1 = R5 = H, Hlg = R4 = R7 =
Br (c); R1 = R4 = H, Hlg = R5 = Cl, R7 = Me (d); R1 = H, Hlg = R4 = R5 = Cl, R7 = Me (e); R1 = H, Hlg = R4 = R5 = Br, R7 = Me (f);
V, R1 = R2 = R3 = R6 = R8 = H, R4 = Me: Hlg = R7 = Cl, R5 = H (a); Hlg = R7 = Br, R5 = H (b); Hlg = R5 = Cl, R7 = Me (c); Hlg = Br,
R5 = H, R7 = Me (d); VI, R1 = R2 = R4 = R6 = R8 = H, R3 = Me: Hlg = R5 = R7 = Cl (a); Hlg = R7 = Br, R5 = H (b); Hlg = R5 = Cl,
R7 = Me (c); Hlg = R5 = Br, R7 = Me (d); VII, R1 = R2 = H, R3 = R4 = Me: Hlg = R7 = Cl, R5 = R6 = R8 = H (a); Hlg = R5 = R7 = Cl,
R6 = R8 = H (b); Hlg = R7 = Br, R5 = R6 = R8 = H (c); Hlg = R5 = Cl, R6 = R8 = H, R7 = Me (d); Hlg = R5 = Br, R6 = R8 = H, R7 =
Me (e); Hlg = R5 = R8 = Cl, R6 = R7 = H (f); Hlg = R5 = R7 = R8 = Cl, R6 = H (g); Hlg = R5 = R6 = R8 = Cl, R7 = H (h); Hlg = R5 =
Br, R6 = R7 = H, R8 = Cl (i); VIII, R1 = R3 = Me, R2 = R4 = H: Hlg = R7 = Cl, R5 = R6 = R8 = H (a); Hlg = R5 = R7 = Cl, R6 = R8 =
H (b); Hlg = R7 = Br, R5 = R6 = R8 = H (c); Hlg = R5 = Cl, R6 = R8 = H, R7 = Me (d); Hlg = R5 = Br, R6 = R8 = H, R7 = Me (e); Hlg =
R5 = R8 = Cl, R6 = R7 = H (f); Hlg = R5 = R6 = R7 = Cl, R8 = H (g); Hlg = R5 = R7 = R8 = Cl, R6 = H (h); Hlg = R5 = Br, R6 = R7 = H,
R8 = Cl (i); IX, R1 = i-Pr, R2 = R4 = H, R3 = Me: Hlg = R5 = R7 = Cl, R6 = R8 = H (a); Hlg = R7 = Br, R5 = R6 = R8 = H (b); Hlg =
R5 = R8 = Cl, R6 = H, R7 = Me (c); X, R1 = R2 = H, R3 = Me, R4 = i-Pr: Hlg = R5 = R7 = Cl, R6 = R8 = H (a); Hlg = R7 = Br, R5 = R6 =
R8 = H (b); Hlg = R5 = R8 = Cl, R6 = H, R7 = Me (c); Hlg = R5 = Br, R6 = R8 = H, R7 = Me (d); XI, R1 = Me, R2 = R4 = H, R3 = i-Pr:
Hlg = R7 = Cl, R5 = R6 = R8 = H (a); Hlg = R5 = R7 = Cl, R6 = R8 = H (b); Hlg = R7 = Br, R5 = R6 = R8 = H (c); Hlg = R5 = Cl, R6 =
R8 = H, R7 = Me (d); Hlg = Br, R5 = R6 = R8 = H, R7 = Me (e); Hlg = R5 = Br, R6 = R8 = H, R7 = Me (f); XII, R1 = R4 = H, R2 = R3 =
Me: Hlg = R5 = R7 = Cl, R6 = R8 = H (a); Hlg = R7 = Br, R5 = R6 = R8 = H (b); Hlg = R5 = Cl, R6 = R8 = H, R7 = Me (c); Hlg = R5 =
R8 = Cl, R6 = R7 = H (d); Hlg = R5 = R6 = R7 = Cl, R8 = H (e); Hlg = R5 = R7 = R8 = Cl, R6 = H (f); Hlg = R5 = Br, R6 = R7 = H, R8 =
Cl (g); XIII, R1 = R3 = R7 = Me, R2 = R4 = R6 = R8 = H, R5 = Cl (a), Br (b); XIV, R1 = i-Pr, R2 = R4 = R6 = R8 = H, R3 = R7 = Me,
R5 = Br; XV, R1 = R4 = R6 = R8 = H, R2 = R3 = R7 = Me, R5 = Cl; XVI, R1 = R4 = Me, R2 = R3 = H: R5 = R6 = R8 = H, R7 = Cl (a);
R5 = R7 = Cl, R6 = R8 = H (b); R5 = R6 = R8 = H, R7 = Br (c); R5 = Cl, R6 = R8 = H, R7 = Me (d); R5 = R8 = Cl, R6 = R7 = H (e); R5 =
R6 = R8 = Cl, R7 = H (f); R5 = R7 = R8 = Cl, R6 = H (g); XVII, R1 = R4 = i-Pr, R2 = R3 = R5 = R6 = R8 = H, R7 = Cl; XVIII, R1 = R4 =
t-Bu, R2 = R3 = H: R5 = R7 = Cl, R6 = R8 = H (a); R7 = Br, R5 = R6 = R8 = H (b); R5 = Cl, R6 = R8 = H, R7 = Me (c); R5 = Br, R6 =
R8 = H, R7 = Me (d).
63:37 in the bromination). Thus the effect of elec-
tronic factor in the halogenation of p-quinone mono-
oxime esters IIIa and IIIb is considerably weaker than
in the halogenation of 4-[aroyl(arylsulfonyl)oxyimino]-
cyclohexa-2,5-dien-1-ones [11, 12] studied previously,
where the isomer ratio was 85:15.
up halogen molecule exclusively at the unsubstituted
C=C bond in the quinoid ring. In the halogenation of
2-methyl derivatives IIIc and IIId, as in the reactions
with 4-aroyl- and 4-arylsulfonylimino derivatives [8],
the Z/E-isomer ratio did not change during the process
within the experimental error and was 58:42 (Va) and
57:43 (Vb) for IIIc and 21:79 (Vc) and 18:82 (Vd)
for IIId. These data indicate that in the halogenation of
4-Arylaminocarbonyloxyimino-2-methyl(3-methyl,
2,3-dimethyl)cyclohexa-2,5-dien-1-ones IIIc–IIIi took
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
833
4-arylaminocarbonyloxyimino derivatives IIIc and
IIId steric factor is more significant than in the reac-
tions with 4-aroylimino and 4-arylsulfonylimino ana-
logs [8], i.e., the effect of the ArNHCO substituent on
the reactivity of C=C bonds in the quinoid ring (in the
syn ans anti positions) of p-quinone monooxime esters
IIIa–IIIz is weaker than in aroyl- and arylsulfonyl-
imino derivatives. In the halogenation of IIId–IIIi,
both steric and electronic factors act in one direction;
therefore, only addition products at the syn-C=C bond
were obtained.
halogen atoms only in the N-aryl fragment, the quinoid
fragment remaining intact. This means that introduc-
tion of alkyl groups deactivates the quinoid ring
toward halogens. In the reactions with 2,6-dialkyl
derivatives IIIt–IIIz no halogenation of the quinoid
ring occurred at all, and the products were only
haloaryl derivatives XVIa–XVIg, XVII, and XVIIIa–
XVIIId.
In order to elucidate the mechanism of halogenation
of p-quinone monooxime esters we previously exam-
ined the bromination of 4-[aroyl(arylsulfonyl)oxy-
mino]-2,3-dimethylcyclohexa-2,5-dien-1-ones in the
presence of LiCl [8]. In the present work we also
examined the bromination of compounds IIIg–IIIi in
the presence of LiCl. As a result, we obtained mixtures
consisting of two compounds. One of these was the
product of addition of one bromine molecule at the
unsubstituted double C=C bond in the quinoid ring
(compounds VIIc, VIIe, and VIIi), while the second
contained one bromine and one chlorine atom. As with
4-(arylsulfonyloxyimino)cyclohexa-2,5-dien-1-ones,
the chlorine atom was attached to the carbon atom in
the ortho position with respect to the carbonyl group
(compounds XIXa–XIXc, Scheme 3). The product
structure suggests that the halogenation of 4-aroyl-
imino-, 4-arylsulfonylimino-, and 4-(arylaminocar-
bonyloxyimino)cyclohexa-2,5-dien-1-ones follows
a common mechanism involving addition of the first
halogen atom at the quinoid C=C bond through inter-
mediate halonium ion and exclusive trans-addition of
the second halogen atom [8].
The halogenation of compounds IIIj–IIIl, IIIo, and
IIIp gave only the corresponding syn-addition prod-
ucts, E isomers VIIIa–VIIIi and XIa–XIf. The halo-
genation of IIIm and IIIn was regioselective with
predominant formation of anti-addition products (the
ratio of the Z and E isomers was about 58:42), indicat-
ing stronger effect of steric factor, as compared to
4-aroylimino- and 4-(arylsulfonyloxyimino)cyclohexa-
2,5-dien-1-ones. The E/Z-isomer ratio for the halo-
genation products of compounds IIIq–IIIs was
~63 :37 (predominant syn addition), but the selectivity
was lower than in the halogenation of N-aroyl and
N-arylsulfonyl analogs [13].
The halogenation of 4-(arylaminocarbonyloxy-
imino)cyclohexa-2,5-dien-1-ones IIIa–IIIz was ac-
companied by electrophilic replacement in the N-aryl
fragment due to the presence of electron-donating NH
group. As might be expected, halogen atom entered
mainly ortho and para positions with respect to the
NH group. On the one hand, the NH group activates
the benzene ring toward electrophilic substitution by
halogen; on the other hand, the presence of the neigh-
boring carbonyl group weakens the activating effects.
Therefore, compounds having one to three halogen
atoms in the aryl fragment were obtained.
Thus the results of the present study showed that,
unlike previously studied 4-[aroyl(arylsulfonyl)imino]-
cyclohexa-2,5-dien-1-ones, the halogenation of
4-(arylaminocarbonyloxyimino)cyclohexa-2,5-dien-1-
ones is affected more strongly by steric rather than
electronic factor due to the presence of NH group
between the aryl fragment and carbonyl group. Intro-
duction of two alkyl groups into the quinoid ring of
Among halogenation products of p-quinone mono-
oxime esters having two alkyl groups in the quinoid
ring we also detected compounds XIII–XVIII with
Scheme 3.
O
R6
R1
R7
O
R1
R2
R4
Cl
Br
R5
R4
Br2, LiCl
O
R8
R3
VIIc, VIIe, VIIi
+
R2
O
N
R3
N
H
N
C(O)NHX
O
IIIg–IIIi
E-XIXa–E-XiXc
XIX, R1 = R2 = H, R3 = R4 = Me: R5 = R6 = R8 = H, R7 = Br (a), R5 = Br, R6 = R8 = H, R7 = Me (b),
R6 = R7 = H, R5 = Br, R8 = Cl (c).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
834
4-(arylaminocarbonyloxyimino)cyclohexa-2,5-dien-1-
ones, especially into positions 2 and 6, deactivates the
quinoid ring toward halogens, whereas the N-aryl
group becomes more reactive than the quinoid frag-
ment due to the presence of NH group.
3-H), 7.15–7.54 m (5H, Ph), 7.73–7.77 d.d (1H, 5-H,
J3,5 = 2.1, J5,6 = 12 Hz), 8.15 br.s (1H, NH); Z isomer:
2.09 br.s (3H, CH3), 6.61 d (1H, 6-H, J5,6 = 12 Hz),
7.15–7.54 m (5H, Ph), 7.22–7.26 d.d (1H, 5-H, J3,5
=
2.4, J5,6 = 12 Hz), 7.65 br.s (1H, 3-H), 8.15 br.s (1H,
NH). Found, %: N 10.95, 11.10. C14H12N2O3. Calculat-
ed, %: N 10.93.
EXPERIMENTAL
1
2-Methyl-4-[(4-methylphenyl)aminocarbonyl-
The H NMR spectra were recorded from solutions
oxyimino]cyclohexa-2,5-dien-1-one (IIId). Yield
in CDCl3 on a Varian VXR-300 spectrometer operating
at 300 MHz; the chemical shifts were determined
relative to tetramethylsilane. The purity of the initial
p-quinone monooxime esters and their halogenation
products was checked by TLC on Silufol UV-254
plates; samples were applied from solutions in chloro-
form, ethanol–chloroform (1:10) was used as eluent,
and spots were visualized under UV light.
1
47%, mp 177–178°C. H NMR spectrum, δ, ppm:
E isomer: 2.07 d (3H, 2-CH3, J = 1.5 Hz), 2.34 s (3H,
CH3C6H4), 6.55 d (1H, 6-H, J5,6 = 10.2 Hz), 7.11 q
(1H, 3-H), 7.17–7.40 d.d (4H, CH3C6H4, J = 8.4 Hz),
7.72–7.75 d.d (1H, 5-H, J3, 5 = 1.5, J5,6 = 10.2 Hz),
8.10 br.s (1H, NH); Z isomer: 2.08 d (3H, 2-CH3, J =
1.5 Hz), 2.34 s (3H, CH3C6H4), 6.61 d (1H, 6-H, J5,6
=
9.9 Hz), 7.17–7.40 d.d (4H, CH3C6H4, J = 8.4 Hz),
7.21–7.24 d.d (1H, 5-H, J3, 5 = 1.8, J5, 6 = 9.9 Hz),
7.64 br.s (1H, 3-H), 8.10 br.s (1H, NH) Found, %:
N 10.35, 10.50 . C15H14N2O3. Calculated, %: N 10.36.
Alkyl and aryl isocyanates IIa–IId were synthe-
sized according to the procedure described in [2].
4-[Aryl(alkyl)aminocarbonyloxyimino]cyclo-
hexa-2,5-dien-1-ones IIIa–IIIab (general procedure).
A suspension of 0.01 mol of p-quinone monooxime
Ia–Ik in 50–55 ml of dioxane was heated to 100°C,
and an equimolar amount of the corresponding alkyl or
aryl isocyanate IIa–IId was slowly added under stir-
ring. After cooling, crystalline solid separated and was
filtered off and recrystallized from ethanol.
3-Methyl-4-(phenylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-one (IIIe). Yield 64%, mp 168–
169°C. 1H NMR spectrum, δ, ppm: 2.34 d (3H, 3-CH3,
J = 1.5 Hz), 6.46 q (1H, 2-H), 6.52–6.56 d.d (1H, 6-H,
J2,6 = 1.5, J5,6 = 12 Hz), 7.16–7.52 m (5H, Ph), 7.82 d
(1H, 5-H, J5,6 = 12 Hz), 8.02 br.s (1H, NH). Found, %:
N 10.80, 10.98. C14H12N2O3. Calculated, %: N 10.93.
4-(Phenylaminocarbonyloxyimino)cyclohexa-
2,5-dien-1-one (IIIa). Yield 40%, mp 166–168°C.
1H NMR spectrum, δ, ppm: 6.59–6.62 d.d (1H, 6-H,
J2,6 = 1.8, J6,5 = 10.5 Hz), 6.62–6.66 d.d (1H, 2-H),
J2,6 = 1.8, J2,3 = 10.5 Hz), 7.16–7.54 m (5H, Ph), 7.31–
7.35 d.d (1H, 5-H, J3,5 = 2.7, J5,6 = 10.5 Hz), 7.80–
7.83 d.d (1H, 3-H, J3,5 = 2.7, J2,3 = 10.5 Hz), 8.04 br.s
(1H, NH). Found, %: N 11.47, 11.53. C13H10N2O3. Cal-
culated, %: N 11.56.
3-Methyl-4-[(4-methylphenyl)aminocarbonyl-
oxyimino]cyclohexa-2,5-dien-1-one (IIIf). Yield
1
55%, mp 200–201°C. H NMR spectrum, δ, ppm:
2.33 br.s (3H, 3-CH3), 2.35 s (3H, CH3C6H4), 6.45 q
(1H, 2-H), 6.51–6.55 d.d (1H, 6-H, J2,6 = 1.5, J5,6
=
10.5 Hz), 7.16–7.38 d.d (4H, CH3C6H4, J = 8.7 Hz),
7.81 d (1H, 5-H, J5,6 = 10.5 Hz), 7.94 br.s (1H, NH).
Found, %: N 10.29, 10.43. C15H14N2O3. Calculated, %:
N 10.36.
4-[(4-Methylphenyl)aminocarbonyloxyimino]-
2,3-Dimethyl-4-(phenylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-one (IIIg). Yield 61%, mp 191–
192°C. 1H NMR spectrum, δ, ppm: 2.07 s (3H, 2-CH3),
2.30 s (3H, 3-CH3), 6.54 d (1H, 6-H, J5,6 = 10.2 Hz),
cyclohexa-2,5-dien-1-one (IIIb). Yield 48%, mp 153–
154°C. H NMR spectrum, δ, ppm: 2.34 s (3H,
1
CH3C6H4), 6.55–6.59 d.d (1H, 6-H, J2,6 = 1.8, J5,6
12 Hz), 6.60–6.63 d.d (1H, 2-H), J2, 6 = 1.8, J2,3
=
=
7.16–7.53 m (5H, Ph), 7.79 d (1H, 5-H, J5, 6
10.2 Hz), 8.10 br.s (1H, NH). C15H14N2O3. Found, %:
N 10.20, 10.32. Calculated, %: N 10.36.
=
9 Hz), 7.17–7.40 d.d (4H, CH3C6H4, J = 8.4 Hz), 7.31–
7.35 d.d (1H, 5-H, J3, 5 = 2.7, J5, 6 = 12 Hz), 7.78–
7.80 d.d (1H, 3-H, J3,5 = 2.7, J2,3 = 9 Hz), 8.07 br.s
(1H, NH). Found, %: N 10.80, 10.98. C14H12N2O3.
Calculated, %: N 10.93.
2,3-Dimethyl-4-[(4-methylphenyl)aminocarbon-
yloxyimino]cyclohexa-2,5-dien-1-one (IIIh). Yield
1
2-Methyl-4-(phenylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-one (IIIc). Yield 36%, mp 141–
142°C. 1H NMR spectrum, δ, ppm: E isomer: 2.09 br.s
(3H, CH3), 6.57 d (1H, 6-H, J5,6 = 12 Hz), 7.12 q (1H,
49%, mp 223–224°C. H NMR spectrum, δ, ppm:
2.06 s (3H, 2-CH3), 2.30 s (3H, 3-CH3), 2.34 s (3H,
CH3C6H4), 6.54 d (1H, 6-H, J5,6 = 10.2 Hz), 7.19–
7.39 d.d (4H, CH3C6H4, J = 8.4 Hz), 7.80 d (1H, 5-H,
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HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
835
J5,6 = 10.2 Hz), 8.02 br.s (1H, NH). Found, %: N 9.72,
9.92. C16H16N2O3. Calculated, %: N 9.85.
4J = 1.2 Hz), 2.34 s (3H, CH3C6H4), 3.06–3.14 m (1H,
i-Pr), 6.42 q (1H, 6-H, 4J = 1.2 Hz), 7.18–7.39 d.d (4H,
CH3C6H4, J = 8.1 Hz), 7.54 br.s (1H, 3-H), 8.13 br.s
(1H, NH). Found, %: N 8.88, 9.01. C18H20N2O3. Cal-
culated, %: N 8.97.
4-[(3-Chlorophenyl)aminocarbonyloxyimino]-
2,3-dimethylcyclohexa-2,5-dien-1-one (IIIi). Yield
1
39%, mp 211–212°C. H NMR spectrum, δ, ppm:
2.07 s (3H, 2-CH3), 2.30 s (3H, 3-CH3), 6.55 d (1H,
5-Isopropyl-2-methyl-4-(phenylaminocarbonyl-
6-H, J5,6 = 10.2 Hz), 7.15–7.17 d.d (1H, 4′-H, J4′,2′
=
oxyimino)cyclohexa-2,5-dien-1-one (IIIo). Yield
1
59%, mp 121–123°C. H NMR spectrum, δ, ppm:
1.2, J4′,5′ = 7.5 Hz), 7.28–7.34 t (1H, 5′-H, J = 7.8 Hz),
7.38–7.41 d.d (1H, 6′-H, J6′,2′ = 1.5, J6′,5′ = 8.1 Hz),
7.60 q (1H, 2′-H), 7.78 d (1H, 5-H, J5,6 = 10.2 Hz),
8.12 br.s (1H, NH). Found, %: N 9.09, 9.25.
C15H13ClN2O3. Calculated, %: N 9.19.
4
1.28 d (6H, i-Pr, J = 6.9 Hz), 2.07 d (3H, 2-CH3, J =
1.2 Hz), 3.27–3.36 m (1H, i-Pr), 6.44 s (1H, 6-H),
7.16–7.53 m (5H, Ph), 7.68 br.s (1H, 3-H), 8.11 br.s
(1H, NH). Found, %: N 9.42, 9.50. C17H18N2O3. Cal-
culated, %: N 9.39.
2,5-Dimethyl-4-(phenylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-one (IIIj). Yield 52%, mp 148–
150°C. 1H NMR spectrum, δ, ppm: 2.07 d (3H, 2-CH3,
5-Isopropyl-2-methyl-4-[(4-methylphenyl)-
aminocarbonyloxyimino]cyclohexa-2,5-dien-1-one
(IIIp). Yield 43%, mp 109–110°C. 1H NMR spectrum,
δ, ppm: 1.27 d (6H, i-Pr, J = 6.9 Hz), 2.06 br.s (3H,
2-CH3), 2.34 s (3H, CH3C6H4), 3.27–3.36 m (1H, i-Pr),
6.44 s (1H, 6-H), 7.18–7.38 d.d (4H, CH3C6H4, J =
8.1 Hz), 7.67 br.s (1H, 3-H), 8.06 br.s (1H, NH). Found,
%: N 8.91, 9.08. C18H20N2O3. Calculated, %: N 8.97.
4
4J = 1.5 Hz), 2.30 d (3H, 5-CH3, J = 1.5 Hz), 6.43 q
4
(1H, 6-H, J = 1.5 Hz), 7.15–7.52 m (5H, Ph), 7.65 q
4
(1H, 3-H, J = 1.5 Hz), 8.12 br.s (1H, NH). Found, %:
N 10.22, 10.46. C15H14N2O3. Calculated, %: N 10.36.
2,5-Dimethyl-4-[(4-methylphenyl)aminocarbon-
yloxyimino]cyclohexa-2,5-dien-1-one (IIIk). Yield
1
68%, mp 138–140°C. H NMR spectrum, δ, ppm:
3,5-Dimethyl-4-(phenylaminocarbonyloxyimino)-
4
2.06 d (3H, 2-CH3, J = 1.5 Hz), 2.29 d (3H, 5-CH3,
cyclohexa-2,5-dien-1-one (IIIq). Yield 64%, mp 125–
1
4J = 1.2 Hz), 2.34 s (3H, CH3C6H4), 6.42 q (1H, 6-H,
4J = 1.5 Hz), 7.18–7.39 d.d (4H, CH3C6H4, J = 8.4 Hz),
7.63 br.s (1H, 3-H), 8.06 br.s (1H, NH). Found, %:
N 9.77, 9.89. C16H16N2O3. Calculated, %: N 9.85.
126°C. H NMR spectrum, δ, ppm: 2.33 br.s (3H,
5-CH3), 2.57 br.s (3H, 3-CH3), 6.31 br.s (1H, 6-H),
6.43 br.s (1H, 2-H), 7.14–7.54 m (5H, Ph), 8.11 br.s
(1H, NH). Found, %: N 10.25, 10.38. C15H14N2O3.
Calculated, %: N 10.36.
4-[(3-Chlorophenyl)aminocarbonyloxyimino]-
3,5-Dimethyl-4-[(4-methylphenyl)aminocarbon-
2,5-dimethylcyclohexa-2,5-dien-1-one (IIIl). Yield
1
62%, mp 193–194°C. H NMR spectrum, δ, ppm:
yloxyimino]cyclohexa-2,5-dien-1-one (IIIr). Yield
4
1
2.07 d (3H, 2-CH3, J = 1.2 Hz), 2.30 d (3H, 5-CH3,
35%, mp 199–200°C. H NMR spectrum, δ, ppm:
4
4
4J = 1.2 Hz), 6.43 q (1H, 3-H, J = 1.5 Hz), 7.13–
2.32 d (3H, 5-CH3, J = 1.2 Hz), 2.34 s (3H,
7.16 d.d (1H, 4′-H, J4′,2′ = 1.2, J4′,5′ = 7.5 Hz), 7.28–
7.33 t (1H, 5′-H, J = 7.8 Hz), 7.37–7.40 d.d (1H, 6′-H,
J6′,2′ = 1.5, J6′,5′ = 8.1 Hz), 7.60 q (1H, 2′-H), 7.62 br.s
(1H, 3-H), 8.17 br.s (1H, NH). Found, %: N 9.15, 9.28.
C15H13ClN2O3. Calculated, %: N 9.19.
CH3C6H4), 2.56 br.s (3H, 3-CH3), 6.30 q (1H, 6-H,
4
4J = 1.2 Hz), 6.41 q (1H, 2-H), J = 1.2 Hz), 7.18–
7.38 d.d (4H, CH3C6H4, J = 8.1 Hz), 8.08 br.s (1H,
NH). Found, %: N 9.79, 9.87. C16H16N2O3. Calculated,
%: N 9.85.
4-[(3-Chlorophenyl)aminocarbonyloxyimino]-
2-Isopropyl-5-methyl-4-(phenylaminocarbonyl-
3,5-dimethylcyclohexa-2,5-dien-1-one (IIIs). Yield
oxyimino)cyclohexa-2,5-dien-1-one (IIIm). Yield
1
1
56%, mp 147–148°C. H NMR spectrum, δ, ppm:
69%, mp 113–114°C. H NMR spectrum, δ, ppm:
4
4
2.33 d (3H, 5-CH3, J = 1.2 Hz), 2.56 d (3H, 3-CH3,
1.15 d (6H, i-Pr, J = 6.9 Hz), 2.30 d (3H, 5-CH3, J =
4J = 0.9 Hz), 6.32 q (1H, 6-H, 4J = 1.2 Hz), 6.43 q (1H,
4
1.2 Hz), 3.06–3.15 m (1H, i-Pr), 6.43 q (1H, 6-H, J =
4
2-H), J = 0.9 Hz), 7.15–7.17 d.d (1H, 4′-H, J4′,2′ = 1.2,
1.2 Hz), 7.16–7.53 m (5H, Ph), 7.54 br.s (1H, 3-H),
8.19 br.s (1H, NH). Found, %: N 9.18, 9.28.
C17H18N2O3. Calculated, %: N 9.39.
J4′,5′ = 7.5 Hz), 7.28–7.34 t (1H, 5′-H, J = 7.8 Hz),
7.38–7.41 d.d (1H, 6′-H, J6′,2′ = 1.5, J6′,5′ = 8.1 Hz),
7.57 q (1H, 2′-H), 8.14 br.s (1H, NH). Found, %:
N 9.15, 9.29. C15H13ClN2O3. Calculated, %: N 9.19.
2-Isopropyl-5-methyl-4-[(4-methylphenyl)amino-
carbonyloxyimino]cyclohexa-2,5-dien-1-one (IIIn).
1
Yield 57%, mp 105–107°C. H NMR spectrum, δ,
2,6-Dimethyl-4-(phenylaminocarbonyloxyimino)-
ppm: 1.15 d (6H, i-Pr, J = 6.9 Hz), 2.29 d (3H, 5-CH3,
cyclohexa-2,5-dien-1-one (IIIt). Yield 59%, mp 156–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
836
1
157°C. H NMR spectrum, δ, ppm: 2.09 br.s (6H,
2-CH3, 6-CH3), 7.05 br.s (1H, 5-H), 7.14–7.54 m
(5H, Ph), 7.62 br.s (1H, 3-H), 8.19 br.s (1H, NH).
Found, %: N 10.25, 10.42. C15H14N2O3. Calculated, %:
N 10.36.
J = 7.8 Hz), 7.52 br.s (1H, 3-H), 8.17 br.s (1H, NH).
Found, %: N 7.62, 7.78. C22H28N2O3. Calculated, %:
N 7.60.
4-(Butylaminocarbonyloxyimino)-2,5-dimethyl-
cyclohexa-2,5-dien-1-one (IIIaa). Yield 8%, mp 136–
1
138°C. H NMR spectrum, δ, ppm: 0.94–0.99 t (3H,
2,6-Dimethyl-4-[(4-methylphenyl)aminocarbon-
yloxyimino]cyclohexa-2,5-dien-1-one (IIIu). Yield
38%, mp 169–170°C. H NMR spectrum, δ, ppm:
2.08 br.s (6H, 2-CH3, 6-CH3), 2.34 s (3H, CH3C6H4),
7.04 q (1H, 5-H), 7.17–7.40 d.d (4H, CH3C6H4, J =
8.1 Hz), 7.61 br.s (1H, 3-H), 8.15 br.s (1H, NH). Found,
%: N 9.75, 9.88. C16H16N2O3. Calculated, %: N 9.85.
CH2CH3), 1.34–1.47 m (2H, CH2CH3), 1.57–1.64 d.d
4
1
(2H, NHCH2CH2), 2.04 d (3H, 2-CH3, J = 0.9 Hz),
4
2.34 d (3H, 5-CH3, J = 0.9 Hz), 3.36–3.40 d.d (2H,
4
NHCH2), 6.31 br.s (1H, NH), 6.40 q (1H, 6-H, J =
4
0.9 Hz), 7.61 q (1H, 3-H, J = 0.9 Hz). Found, %:
N 11.10, 11.25. C13H18N2O3. Calculated, %: N 11.19.
4-(tert-Butylaminocarbonyloxyimino)-2,6-di-
methylcyclohexa-2,5-dien-1-one (IIIab). Yield 15%,
4-[(3-Chlorophenyl)aminocarbonyloxyimino]-
2,6-dimethylcyclohexa-2,5-dien-1-one (IIIv). Yield
1
1
mp 136–138°C. H NMR spectrum, δ, ppm: 1.43 s
34%, mp 168–169°C. H NMR spectrum, δ, ppm:
4
4
(9H, t-Bu), 2.06 d (3H, 2-CH3, J = 1.2 Hz), 2.07 d
2.10 d (3H, 2-CH3, J = 1.5 Hz), 2.09 d (3H, 6-CH3,
4
4J = 1.5 Hz), 7.03 br.s (1H, 5-H), 7.13–7.15 d.d (1H,
4′-H, J4′,2′ = 1.2, J4′,5′ = 7.5 Hz), 7.27–7.32 t (1H, 5′-H,
(3H, 6-CH3, J = 1.2 Hz), 6.15 br.s (1H, NH), 6.99 q
(1H, 5-H), 7.57 q (1H, 3-H). Found, %: N 11.20,
11.35. C13H18N2O3. Calculated, %: N 11.19.
J = 7.8 Hz), 7.39–7.41 d.d (1H, 6′-H, J6′,2′ = 1.5, J6′,5′
=
8.1 Hz), 7.61 q (1H, 2′-H), 7.62 br.s (1H, 3-H), 8.25 br.s
(1H, NH). Found, %: N 9.22, 9.38. C15H13ClN2O3.
Calculated, %: N 9.19.
Chlorination of 4-(arylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-ones IIIa–IIIz (general proce-
dure). Gaseous chlorine was passed at a flow rate of
15–20 ml/min through a solution of 5 mmol of com-
pound IIIa–IIIz in 3 ml of acetic acid or chloroform,
heated to 50–60°C, until complete saturation. The
chlorination products were isolated by removal of the
solvent to dryness (chloroform) or precipitation with
water (acetic acid) and were recrystallized from ben-
zene–hexane (1:1). The yields, melting points, and
elemental compositions are given below only for prod-
ucts isolated as individual substances.
2,6-Diisopropyl-4-(phenylaminocarbonyloxy-
imino)cyclohexa-2,5-dien-1-one (IIIw). Yield 61%,
1
mp 168–169°C. H NMR spectrum, δ, ppm: 1.16 d
(12H, i-Pr), 3.08–3.20 m (2H, 2-CH, 6-CH), 6.98 br.s
(1H, 5-H), 7.14–7.56 m (5H, Ph), 7.51 br.s (1H, 3-H),
8.25 br.s (1H, NH). Found, %: N 8.48, 9.62.
C19H22N2O3. Calculated, %: N 8.58.
2,6-Diisopropyl-4-[(4-methylphenyl)aminocar-
bonyloxyimino]cyclohexa-2,5-dien-1-one (IIIx).
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
1
Yield 45%, mp 136–138°C. H NMR spectrum, δ,
1
bonyloxyimino]cyclohex-2-en-1-one (IVa). H NMR
ppm: 1.16 d (12H, i-Pr), 2.35 s (3H, CH3C6H4), 3.08–
3.20 m (2H, 2-CH, 6-CH), 6.98 br.s (1H, 5-H), 7.19–
7.42 d.d (4H, CH3C6H4, J = 8.1 Hz), 7.52 br.s (1H,
3-H), 8.18 br.s (1H, NH). Found, %: N 8.12, 8.20.
C20H24N2O3. Calculated, %: N 8.23.
spectrum, δ, ppm: E isomer (36%): 4.47 d (1H, 6-H,
J5,6 = 2.4 Hz), 5.69 br.s (1H, 5-H), 6.51 d (1H, 2-H),
J2,3 = 10.5 Hz), 7.19–7.23 d.d (1H, 3-H, J3,5 = 1.8,
J2,3 = 10.5 Hz), 7.32–7.35 d.d (1H, 5′-H, J5′,3′ = 1.8,
J5′,6′ = 9 Hz), 7.45 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 8.18 d
(1H, 6′-H, J5′,6′ = 9 Hz), 8.56 br.s (1H, NH); Z isomer
(28%): 4.77 d (1H, 6-H, J5,6 = 3 Hz), 5.18 q (1H, 5-H),
6.46 d (1H, 2-H), J2,3 = 11.7 Hz), 7.32–7.35 d.d (1H,
2,6-Di-tert-butyl-4-(phenylaminocarbonyloxy-
imino)cyclohexa-2,5-dien-1-one (IIIy). Yield 64%,
1
mp 136–138°C. H NMR spectrum, δ, ppm: 1.31 s
(18H, t-Bu), 7.00 d (1H, 5-H, J3,5 = 2.4 Hz), 7.14–
7.56 m (5H, Ph), 7.53 br.s (1H, 3-H), 8.24 br.s (1H,
NH). Found, %: N 7.82, 7.98. C21H26N2O3. Calculated,
%: N 7.90.
5′-H, J5′,3′ = 1.8, J5′,6′ = 9 Hz), 7.45 d (1H, 3′-H, J5′,3′
1.8 Hz), 7.68–7.71 d.d (1H, 3-H, J3,5 = 1.8 Hz), 8.18 d
(1H, 6′-H, J5′,6′ = 9 Hz), 8.39 br.s (1H, NH).
=
2,5,6-Trichloro-4-[(2,4-dichlorophenyl)aminocar-
1
2,6-Di-tert-butyl-4-[(4-methylphenyl)aminocar-
bonyloxyimino]cyclohex-2-en-1-one (IVb). H NMR
bonyloxyimino]cyclohexa-2,5-dien-1-one (IIIz).
Yield 62%, mp 136–138°C. H NMR spectrum, δ,
ppm: 1.31 s (18H, t-Bu), 2.34 s (3H, CH3C6H4), 7.00 d
(1H, 5-H, J3,5 = 2.1 Hz), 7.18–7.42 d.d (4H, CH3C6H4,
spectrum, δ, ppm: E isomer (25%): 4.47 d (1H, 6-H,
1
J5,6 = 3.3 Hz), 5.62 q (1H, 5-H), 7.29 d (1H, 3-H, J3,5
1.5 Hz), 7.32–7.35 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′
=
=
9 Hz), 7.45 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 8.21 d (1H,
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HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
837
6′-H, J5′, 6′ = 9 Hz), 8.56 br.s (1H, NH); Z isomer
(11%): 4.77 d (1H, 6-H, J5,6 = 2.4 Hz), 5.16 q (1H,
5-H), 7.32–7.35 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′ = 9 Hz),
7.45 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 7.90 d (1H, 3-H,
J3,5 = 1.5 Hz), 8.21 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.49 br.s
(1H, NH).
6′-H, J5′, 6′ = 9 Hz), 8.58 br.s (1H, NH); Z isomer
(21%): 2.12 br.s (3H, 2-CH3), 2.33 s (3H, CH3C6H3),
4.59 br.s (1H, 6-H, J5,6 = 3.3 Hz), 5.07 q (1H, 5-H,
J5,3 = 1.5 Hz), 7.12–7.15 d.d (1H, 5′-H, J5′,3′ = 1.8,
J5′,6′ = 9 Hz), 7.25 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 7.48 q
(1H, 3-H), 8.09 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.58 br.s
(1H, NH).
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]cyclohex-2-en-1-one (IVd).
1H NMR spectrum, δ, ppm: E isomer (38%): 2.34 s
(3H, CH3C6H3), 4.47 d (1H, 6-H, J5,6 = 2.7 Hz), 5.70 q
(1H, 5-H), 6.50 d (1H, 2-H), J2,3 = 10,5 Hz), 7.17–
7.20 d.d (1H, 3-H, J3,5 = 2.7 Hz), 7.13–7.15 d.d (1H,
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-3-methylcyclohex-2-en-1-one (VIa).
1
Yield 91%, mp 156–157°C. H NMR spectrum, δ,
ppm: 2.33 br.s (3H, 3-CH3), 4.45 q (1H, 6-H, J5,6 = 3,
J2,6 = 1.2 Hz), 5.76 d (1H, 6-H, J5,6 = 3 Hz), 6.37 br.s
(1H, 2-H), 7.32–7.35 d.d (1H, 5′-H, J5′,3′ = 2.1, J5′,6′
=
5′-H, J5′,3′ = 1.8, J5′,6′ = 9 Hz), 7.24 d (1H, 3′-H, J5′,3′
=
9 Hz), 7.45 d (1H, 3′-H, J5′,3′ = 2.1 Hz), 8.26 d (1H, 6′-H,
J5′,6′ = 9 Hz), 8.88 br.s (1H, NH). Found, %: Cl 35.80,
35.92. C14H10Cl4N2O3. Calculated, %: Cl 35.81.
1.8 Hz), 8.08 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.47 br.s (1H,
NH); Z isomer (19%): 2.34 s (3H, CH3C6H3), 4.76 d
(1H, 6-H, J5,6 = 3 Hz), 5.17 q (1H, 5-H), 6.45 d (1H,
2-H), J2,3 = 10.5 Hz), 7.13–7.15 d.d (1H, 5′-H, J5′,3′
=
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]-3-methylcyclohex-2-en-1-
one (VIc). Yield 95%, mp 157–158°C. 1H NMR spec-
trum, δ, ppm: 2.33 br.s (3H, 3-CH3), 2.33 s (3H,
CH3C6H3), 4.44 q (1H, 6-H, J2,6 = 0.9 Hz), 5.76 d (1H,
6-H, J5,6 = 2.7 Hz), 6.36 br.s (1H, 2-H), 7.13–7.16 d.d
(1H, 5′-H, J5′,3′ = 1.8, J5′,6′ = 8.4 Hz), 7.24 br.s (1H,
3′-H), 8.13 d (1H, 6′-H, J5′,6′ = 8.4 Hz), 8.83 br.s (1H,
NH). Found, %: Cl 28.34, 28.45. C15H13Cl3N2O3. Cal-
culated, %: Cl 28.31.
1.8, J5′,6′ = 9 Hz), 7.24 d (1H, 3′-H, J5′,3′ = 1.8 Hz),
8.08 d (1H, 6′-H, J5′,6′ = 9 Hz), 7.68–7.72 d.d (1H, 3-H,
J3,5 = 1.5 Hz), 8.47 br.s (1H, NH).
2,5,6-Trichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]cyclohex-2-en-1-one (IVe).
1H NMR spectrum, δ, ppm: E isomer (24%): 2.34 s
(3H, CH3C6H3), 4.47 d (1H, 6-H, J5,6 = 2.7 Hz), 5.64 q
(1H, 5-H), 7.13–7.15 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′
=
9 Hz), 7.28 d (1H, 3-H, J3,5 = 1.8 Hz), 7.24 d (1H,
3′-H, J5′,3′ = 1.8 Hz), 8.08 d (1H, 6′-H, J5′,6′ = 9 Hz),
8.48 br.s (1H, NH); Z isomer (19%): 2.34 s (3H,
CH3C6H3), 4.76 d (1H, 6-H, J5,6 = 3 Hz), 5.13 q (1H,
5-H), 7.13–7.15 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′ = 9 Hz),
7.24 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 7.91 d (1H, 3-H,
J3,5 = 1.2 Hz), 8.08 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.48 br.s
(1H, NH).
5,6-Dichloro-4-[(4-chlorophenyl)aminocarbonyl-
oxyimino]-2,3-dimethylcyclohex-2-en-1-one (VIIa).
1H NMR spectrum, δ, ppm: 2.09 br.s (3H, 2-CH3),
2.29 br.s (3H, 3-CH3), 4.46 d (1H, 6-H, J5,6 = 2.7 Hz),
5.72 d (1H, 6-H), 7.35–7.47 d.d (4H, C6H4, J = 9 Hz),
9.00 br.s (1H, NH).
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-2,3-dimethylcyclohex-2-en-1-one
5,6-Dichloro-4-[(4-chlorophenyl)aminocarbonyl-
oxyimino]-2-methylcyclohex-2-en-1-one (Va).
1
(VIIb). H NMR spectrum, δ, ppm: 2.11 br.s (3H,
1H NMR spectrum, δ, ppm: E isomer (43%): 2.09 d
2-CH3), 2.30 br.s (3H, 3-CH3), 4.49 d (1H, 6-H, J5,6
2.7 Hz), 5.75 d (1H, 5-H), 7.31–7.34 d.d (1H, 5′-H,
J5′,3′ = 2.4, J5′,6′ = 12 Hz), 7.45 d (1H, 3′-H, J5′,3′
=
4
(3H, 2-CH3, J = 1.2 Hz), 4.42 d (1H, 6-H, J5,6
2.7 Hz), 5.60 br.s (1H, 5-H), 6.99 q (1H, 3-H, J5,3
=
=
=
1.5 Hz), 7.35–7.47 d.d (4H, C6H4, J = 11.7 Hz),
8.15 br.s (1H, NH); Z isomer (57%): 2.09 d (3H, 2-CH3,
4J = 1.2 Hz), 4.57 d (1H, 6-H, J5,6 = 3.3 Hz), 5.09 q
(1H, 5-H, J5,3 = 1.5 Hz), 7.35–7.47 d.d (4H, C6H4, J =
11.7 Hz), 7.50 br.s (1H, 3-H), 8.11 br.s (1H, NH).
2.4 Hz), 8.27 d (1H, 6′-H, J5′,6′ = 12 Hz), 8.96 br.s
(1H, NH).
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]-2,3-dimethylcyclohex-2-
en-1-one (VIId). Yield 59%, mp 114–115°C. 1H NMR
spectrum, δ, ppm: 2.10 br.s (3H, 2-CH3), 2.31 br.s
(3H, 3-CH3), 2.34 s (3H, CH3C6H3), 4.49 d (1H, 6-H,
J5,6 = 2.7 Hz), 5.77 d (1H, 5-H), 7.13–7.16 d.d (1H,
5′-H, J5′,3′ = 2.1, J5′,6′ = 9 Hz), 7.24 d (1H, 3′-H),
8.15 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.90 br.s (1H, NH).
Found, %: Cl 27.26, 27.34. C16H15Cl3N2O3. Calculat-
ed, %: Cl 27.29.
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]-2-methylcyclohex-2-en-1-
one (Vc). 1H NMR spectrum, δ, ppm: E isomer (79%):
2.12 br.s (3H, 2-CH3), 2.33 s (3H, CH3C6H3), 4.48 d
(1H, 6-H, J5,6 = 2.7 Hz), 5.68 br.s (1H, 5-H), 6.96 q
(1H, 3-H), 7.12–7.15 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′
=
9 Hz), 7.25 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 8.09 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
838
6.38 br.s (1H, 2-H), 7.08–7.11 d.d (1H, 4′-H, J4′,6′
=
5,6-Dichloro-4-[(2,5-dichlorophenyl)aminocar-
2.4, J4′,3′ = 8.4 Hz), 7.34 d (1H, 3′-H, J4′,3′ = 8.4 Hz),
8.39 d (1H, 6′-H, J4′,6′ = 2.4 Hz), 9.02 br.s (1H, NH).
bonyloxyimino]-2,3-dimethylcyclohex-2-en-1-one
(VIIf). H NMR spectrum, δ, ppm: 2.11 s (3H, 2-CH3),
1
2.31 s (3H, 3-CH3), 4.50 d (1H, 6-H, J5,6 = 3 Hz),
5.76 d (1H, 5-H), 7.08–7.11 d.d (1H, 4′-H, J4′,6′ = 2.4,
J3′,4′ = 9 Hz), 7.36 d (1H, 3′-H), 8.39 d (1H, 6′-H),
8.98 br.s (1H, NH).
5,6-Dichloro-3,6-dimethyl-4-[(2,3,4-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
one (VIIIg). H NMR spectrum, δ, ppm: 1.89 s (3H,
6-CH3), 2.31 br.s (3H, 3-CH3), 5.75 s (1H, 5-H),
6.38 br.s (1H, 2-H), 7.46 d (1H, 5′-H, J5′,6′ = 9 Hz),
8.26 d (1H, 6′-H, J5′,6′ = 9 Hz), 9.05 br.s (1H, NH).
1
5,6-Dichloro-2,3-dimethyl-4-[(2,4,5-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
1
one (VIIg). H NMR spectrum, δ, ppm: 2.09 s (3H,
5,6-Dichloro-3,6-dimethyl-4-[(2,4,5-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
2-CH3), 2.30 s (3H, 3-CH3), 4.47 d (1H, 6-H, J5,6
=
1
3 Hz), 5.70 d (1H, 5-H), 7.54 s (1H, 3′-H), 8.51 s (1H,
6′-H), 9.04 br.s (1H, NH).
one (VIIIh). H NMR spectrum, δ, ppm: 1.89 s (3H,
6-CH3), 2.31 br.s (3H, 3-CH3), 5.75 s (1H, 5-H),
6.38 br.s (1H, 2-H), 7.54 s (1H, 3′-H), 8.51 s (1H,
6′-H), 8.98 br.s (1H, NH).
5,6-Dichloro-2,3-dimethyl-4-[(2,3,5-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
1
one (VIIh). H NMR spectrum, δ, ppm: 2.10 s (3H,
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-6-isopropyl-3-methylcyclohex-2-en-
1-one (IXa). 1H NMR spectrum, δ, ppm: 1.22–1.24 d.d
[6H, 6-CH(CH3)2, J = 6.6 Hz], 2.27 d (3H, 3-CH3, 4J =
1.5 Hz), 2.67–2.74 m (1H, 6-CH), 5.72 s (1H, 5-H),
2-CH3), 2.30 s (3H, 3-CH3), 4.49 d (1H, 6-H, J5,6
2.4 Hz), 5.74 d (1H, 5-H), 7.39 d (1H, 4′-H, J4′,6′
2.1 Hz), 7.71 d (1H, 6′-H), 9.02 br.s (1H, NH).
=
=
5,6-Dichloro-4-[(4-chlorophenyl)aminocarbonyl-
oxyimino]-3,6-dimethylcyclohex-2-en-1-one (VIIIa).
6.32 br.s (1H, 2-H), 7.31–7.34 d.d (1H, 5′-H, J5′,3′
=
1
2.1, J5′,6′ = 8.7 Hz), 7.44 d (1H, 3′-H, J5′,3′ = 2.1 Hz),
8.28 d (1H, 6′-H, J5′,6′ = 8.7 Hz), 9.06 br.s (1H, NH).
Yield 87%, mp 188–189°C. H NMR spectrum,
4
δ, ppm: 1.87 s (3H, 6-CH3), 2.30 d (3H, 3-CH3, J =
4
1.2 Hz), 5.72 s (1H, 5-H), 6.35 q (1H, 2-H), J =
5,6-Dichloro-4-[(2,5-dichloro-4-methylphenyl)-
aminocarbonyloxyimino]-6-isopropyl-3-methyl-
1.2 Hz), 7.35–7.46 d.d (4H, C6H4, J = 8.7 Hz),
7.97 br.s (1H, NH). Found, %: Cl 28.23, 28.31.
C15H13Cl3N2O3. Calculated, %: Cl 28.31.
1
cyclohex-2-en-1-one (IXc). H NMR spectrum, δ,
ppm: 1.21–1.23 d.d [6H, 6-CH(CH3)2, J = 8.4 Hz],
2.09 s (3H, CH3C6H2), 2.23 br.s (3H, 3-CH3), 2.61–
2.78 m (1H, 6-CH), 5.66 s (1H, 5-H), 6.31 br.s (1H,
2-H), 7.27 s (1H, 3′-H), 7.36 s (1H, 6′-H), 8.42 br.s
(1H, NH).
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-3,6-dimethylcyclohex-2-en-1-one
1
(VIIIb). Yield 86%, mp 111–112°C. H NMR spec-
trum, δ, ppm: 1.89 s (3H, 6-CH3), 2.31 d (3H, 3-CH3,
4
4J = 1.2 Hz), 5.75 s (1H, 5-H), 6.38 q (1H, 2-H), J =
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-2-isopropyl-5-methylcyclohex-2-en-
1-one (Xa). 1H NMR spectrum, δ, ppm: 1.12–1.15 d.d
[6H, 2-CH(CH3)2, J = 6.9 Hz], 2.13 br.s (3H, 5-CH3),
3.03–3.12 m (1H, 2-CH), 4.47 s (1H, 6-H), 7.31–
7.34 d.d (1H, 5′-H, J5′,3′ = 2.1, J5′,6′ = 8.7 Hz), 7.42 br.s
(1H, 3-H), 7.44 d (1H, 3′-H, J5′,3′ = 2.1 Hz), 8.28 d
(1H, 6′-H, J5′,6′ = 8.7 Hz), 9.03 br.s (1H, NH).
1.2 Hz), 7.31–7.35 d.d (1H, 5′-H, J5′,3′ = 2.7, J5′,6′
=
11.7 Hz), 7.44 d (1H, 3′-H, J5′,3′ = 2.7 Hz), 8.28 d
(1H, 6′-H, J5′,6′ = 11.7 Hz), 8.97 br.s (1H, NH). Found,
%: Cl 34.55, 34.68. C15H12Cl4N2O3. Calculated, %:
Cl 34.58.
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]-3,6-dimethylcyclohex-2-
en-1-one (VIIId). 1H NMR spectrum, δ, ppm: 1.89 s
5,6-Dichloro-4-[(2,5-dichloro-4-methylphenyl)-
aminocarbonyloxyimino]-2-isopropyl-5-methyl-
cyclohex-2-en-1-one (Xc). 1H NMR spectrum, δ, ppm:
1.11–1.14 d.d [6H, 2-CH(CH3)2, J = 9 Hz], 2.09 s (3H,
5-CH3), 2.09 s (3H, CH3C6H2), 3.01–3.12 m (1H,
2-CH), 4.45 s (1H, 6-H), 7.27 s (1H, 3′-H), 7.35 br.s
(1H, 3-H), 7.36 s (1H, 6′-H), 8.42 br.s (1H, NH).
4
(3H, 6-CH3), 2.31 d (3H, 3-CH3, J = 0.9 Hz), 2.33 s
(3H, CH3C6H3), 5.77 s (1H, 5-H), 6.37 q (1H, 5-H),
7.13–7.16 d.d (1H, 5′-H, J5′,3′ = 2.1, J5′,6′ = 9 Hz),
7.23 br.s (1H, 3′-H), 8.15 d (1H, 6′-H, J5′,6′ = 9 Hz),
8.92 br.s (1H, NH).
5,6-Dichloro-4-[(2,5-dichlorophenyl)aminocar-
bonyloxyimino]-3,6-dimethylcyclohex-2-en-1-one
5,6-Dichloro-4-[(4-chlorophenyl)aminocarbonyl-
oxyimino]-3-isopropyl-6-methylcyclohex-2-en-1-one
(XIa). Yield 97%, mp 158–160°C. 1H NMR spectrum,
1
(VIIIf). H NMR spectrum, δ, ppm: 1.89 s (3H,
6-CH3), 2.30 br.s (3H, 3-CH3), 5.75 s (1H, 5-H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
839
δ, ppm: 1.25–1.31 d.d [6H, 3-CH(CH3)2, J = 8.4 Hz],
1.87 s (3H, 6-CH3), 3.18–3.27 m (1H, 3-CH), 5.78 s
(1H, 5-H), 6.32 s (1H, 2-H), 7.36–7.47 d.d (4H, C6H4,
J = 9 Hz), 7.89 br.s (1H, NH). Found, %: Cl 26.38,
26.45. C17H17Cl3N2O3. Calculated, %: Cl 26.35.
5-CH3), 2.55 br.s (3H, 3-CH3), 4.39 s (1H, 6-H),
6.24 br.s (1H, 2-H), 7.08–7.11 d.d (1H, 4′-H, J4′,6′
=
2.4, J4′,3′ = 9 Hz), 7.35 d (1H, 3′-H, J4′,3′ = 9 Hz), 8.38 d
(1H, 6′-H, J4′,6′ = 2.4 Hz), 9.04 br.s (1H, NH).
5,6-Dichloro-3,5-dimethyl-4-[(2,3,4-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-3-isopropyl-6-methylcyclohex-2-en-
1
one (XIIe). H NMR spectrum, δ, ppm: 2.13 s (3H,
1
5-CH3), 2.55 br.s (3H, 3-CH3), 4.39 s (1H, 6-H),
6.24 br.s (1H, 2-H), 7.46 d (1H, 5′-H, J5′,6′ = 9 Hz),
8.24 d (1H, 6′-H, J5′,6′ = 9 Hz), 9.00 br.s (1H, NH).
1-one (XIb). Yield 92%, mp 161–162°C. H NMR
spectrum, δ, ppm: 1.26–1.32 d.d [6H, 3-CH(CH3)2, J =
7.8 Hz], 1.89 s (3H, 6-CH3), 3.19–3.31 m (1H, 3-CH),
5.81 s (1H, 5-H), 6.35 s (1H, 2-H), 7.32–7.35 d.d (1H,
5,6-Dichloro-3,5-dimethyl-4-[(2,4,5-trichloro-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
5′-H, J5′,3′ = 2.4, J5′,6′ = 9 Hz), 7.45 d (1H, 3′-H, J5′,3′
=
1
2.4 Hz), 8.28 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.91 br.s
(1H, NH). Found, %: Cl 32.29, 32.41. C17H16Cl4N2O3.
Calculated, %: Cl 32.37.
one (XIIf). H NMR spectrum, δ, ppm: 2.13 s (3H,
5-CH3), 2.55 br.s (3H, 3-CH3), 4.39 s (1H, 6-H),
6.24 br.s (1H, 2-H), 7.54 s (1H, 3′-H), 8.50 s (1H,
6′-H), 8.96 br.s (1H, NH).
5,6-Dichloro-4-[(2-chloro-4-methylphenyl)-
aminocarbonyloxyimino]-3-isopropyl-6-methylcy-
clohex-2-en-1-one (XId). Yield 55%, mp 184–185°C.
1H NMR spectrum, δ, ppm: 1.26–1.32 d.d [6H,
3-CH(CH3)2, J = 7.8 Hz], 1.88 s (3H, 6-CH3), 2.34 s
(3H, CH3C6H3), 3.21–3.33 m (1H, 3-CH), 5.82 s (1H,
5-H), 6.34 s (1H, 2-H), 7.13–7.16 d.d (1H, 5′-H,
J5′,3′ = 2.1, J5′,6′ = 8.1 Hz), 7.24 br.s (1H, 3′-H), 8.15 d
(1H, 6′-H, J5′,6′ = 8.1 Hz), 8.85 br.s (1H, NH). Found,
%: Cl 25.35, 25.49. C18H19Cl3N2O3. Calculated, %:
Cl 25.46.
4-[(2-Chloro-4-methylphenyl)aminocarbonyl-
oxyimino]-2,5-dimethylcyclohexa-2,5-dien-1-one
1
(XIIIa). H NMR spectrum, δ, ppm: 2.09 d (3H,
2-CH3, 4J = 1.5 Hz), 2.33 br.s (3H, 5-CH3), 2.33 s (3H,
4
CH3C6H3), 6.44 q (3H, 5-CH3, J = 1.5 Hz), 7.13–
7.16 d.d (1H, 5′-H, J5′,3′ = 2.1, J5′,6′ = 9 Hz), 7.23 br.s
(1H, 3′-H), 7.66 d (1H, 3-H), 8.15 d (1H, 6′-H, J5′,6′
=
9 Hz), 9.05 br.s (1H, NH).
4-[(2-Chloro-4-methylphenyl)-3,5-dimethyl-
aminocarbonyloxyimino]cyclohexa-2,5-dien-1-one
1
(XV). NNMR spectrum, δ, ppm: 2.37 br.s (3H,
5,6-Dichloro-4-[(2,4-dichlorophenyl)aminocar-
bonyloxyimino]-3,5-dimethylcyclohex-2-en-1-one
5-CH3), 2.34 s (3H, CH3C6H3), 2.55 br.s (3H, 3-CH3),
6.47 br.s (1H, 6-H), 6.57 br.s (1H, 2-H), 7.13–7.16 d.d
(1H, 5′-H, J5′,3′ = 2.1, J5′,6′ = 8.1 Hz), 7.24 br.s (1H,
3′-H), 8.13 d (1H, 6′-H, J5′,6′ = 8.1 Hz), 8.87 br.s
(1H, NH).
1
(XIIa). H NMR spectrum, δ, ppm: E isomer (64%):
2.13 s (3H, 5-CH3), 2.55 br.s (3H, 3-CH3), 4.39 s (1H,
6-H), 6.23 br.s (1H, 2-H), 7.34–7.37 d.d (1H, 5′-H,
J5′,3′ = 2.4, J5′,6′ = 7.8 Hz), 7.44 d (1H, 3′-H, J5′,3′
=
2.4 Hz), 8.26 d (1H, 6′-H, J5′,6′ = 7.8 Hz), 8.97 br.s
(1H, NH); Z isomer (36%): 2.14 s (3H, 5-CH3), 2.52 s
(3H, 3-CH3), 4.28 s (1H, 6-H), 6.39 br.s (1H, 2-H),
7.34–7.37 d.d (1H, 5′-H, J5′,3′ = 2.4, J5′,6′ = 7.8 Hz),
7.44 d (1H, 3′-H, J5′,3′ = 2.4 Hz), 8.26 d (1H, 6′-H,
J5′,6′ = 7.8 Hz), 8.97 br.s (1H, NH).
4-[(4-Chlorophenyl)aminocarbonyloxyimino]-
2,6-dimethylcyclohexa-2,5-dien-1-one (XVIa).
4
1H NMR spectrum, δ, ppm: 2.09 d (3H, 2-CH3, J =
4
1.5 Hz), 2.10 d (3H, 6-CH3, J = 1.5 Hz), 7.03 q (1H,
5-H, 4J = 1.5 Hz), 7.33–7.49 d.d (4H, C6H4, J = 9 Hz),
7.62 q (1H, 3-H), 8.20 br.s (1H, NH).
5,6-Dichloro-3,5-dimethyl-4-[(2-chloro-4-methyl-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
one (XIIc). H NMR spectrum, δ, ppm: 2.13 s (3H,
5-CH3), 2.34 s (3H, CH3C6H3), 2.55 br.s (3H, 3-CH3),
4.39 s (1H, 6-H), 6.22 br.s (1H, 2-H), 7.13–7.16 d.d
(1H, 5′-H, J5′,3′ = 2.1, J5′,6′ = 8.1 Hz), 7.24 br.s
(1H, 3′-H), 8.13 d (1H, 6′-H, J5′,6′ = 8.1 Hz), 8.96 br.s
(1H, NH).
4-[(2,4-Dichlorophenyl)aminocarbonyloxy-
imino]-2,6-dimethylcyclohexa-2,5-dien-1-one
1
1
(XVIb). H NMR spectrum, δ, ppm: 2.10 d (3H,
4
4
2-CH3, J = 1.5 Hz), 2.11 d (3H, 6-CH3, J = 1.5 Hz),
7.03 q (1H, 5-H, 4J = 1.5 Hz), 7.30–7.33 d.d (1H, 5′-H,
J5′,3′ = 2.4, J5′,6′ = 9 Hz), 7.43 d (1H, 3′-H, J5′,3′
2.4 Hz), 7.62 q (1H, 3-H), 8.24 d (1H, 6′-H, J5′,6′
9 Hz), 8.88 br.s (1H, NH).
=
=
5,6-Dichloro-4-[(2,5-dichlorophenyl)aminocar-
bonyloxyimino]-3,5-dimethylcyclohex-2-en-1-one
(XIId). H NMR spectrum, δ, ppm: 2.12 s (3H,
4-[(2-Chloro-4-methylphenyl)aminocarbonyloxy-
imino]-2,6-dimethylcyclohexa-2,5-dien-1-one
(XVId). Yield 91%, mp 146–149°C. H NMR spec-
1
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
840
trum, δ, ppm: 2.09 d (3H, 2-CH3, J = 1.5 Hz), 2.11 d
(3H, 6-CH3, J = 1.5 Hz), 2.33 s (3H, CH3C6H3),
CH3C6H3), 6.97 d (1H, 5-H, J3,5 = 1.8 Hz), 7.12–
7.15 d.d (1H, 5′-H, J5′,3′ = 1.5, J5′,6′ = 8.4 Hz), 7.24 br.s
(1H, 3′-H), 7.53 br.s (1H, 3-H), 8.10 d (1H, 6′-H,
J5′,6′ = 8.4 Hz), 8.73 br.s (1H, NH). Found, %: Cl 8.73,
8.89. C22H27ClN2O3. Calculated, %: Cl 8.80.
4
7.05 q (1H, 5-H, J3,5 = 1.2 Hz), 7.12–7.15 d.d (1H,
5′-H, J5′,3′ = 1.5, J5′,6′ = 9 Hz), 7.23 br.s (1H, 3′-H),
7.63 q (1H, 3-H), 8.11 d (1H, 6′-H, J5′,6′ = 9 Hz),
8.78 br.s (1H, NH). Found, %: Cl 11.06, 11.22.
C16H15ClN2O3. Calculated, %: Cl 11.12.
Bromination of 4-(arylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-ones Ia–Iz (general procedure).
A solution of 5 mmol of compound IIIa–IIIz in 3 ml
of acetic acid or chloroform was heated to the boiling
point, a solution of 25 mmol of bromine in 2 ml of the
same solvent, heated to 50–60°C, was added dropwise
under vigorous stirring (the molar ratio III–Br2 was
1:5), and the mixture was vigorously stirred on heating
under reflux over a period of 5–10 min. The mixture
was cooled, and the precipitate was filtered off and
recrystallized from benzene–hexane (1:1). The yields,
melting points, and elemental compositions are given
only for products isolated as individual substances.
4-[(2,5-Dichlorophenyl)aminocarbonyloxy-
imino]-2,6-dimethylcyclohexa-2,5-dien-1-one
1
(XVIe). H NMR spectrum, δ, ppm: 2.09 d (3H,
4
4
2-CH3, J = 1.2 Hz), 2.10 d (3H, 6-CH3, J = 1.5 Hz),
7.02 q (1H, 5-H, J3,5 = 0.9 Hz), 7.06–7.09 d.d (1H,
4′-H, J4′,6′ = 2.1, J4′,3′ = 9 Hz), 7.34 d (1H, 3′-H, J4′,3′
9 Hz), 7.60 q (1H, 3-H), 8.36 d (1H, 6′-H, J4′,6′
2.1 Hz), 8.28 br.s (1H, NH).
=
=
2,6-Dimethyl-4-[(2,3,5-trichlorophenyl)amino-
carbonyloxyimino]cyclohexa-2,5-dien-1-one (XVIf).
4
1H NMR spectrum, δ, ppm: 2.10 d (3H, 2-CH3, J =
4
1.2 Hz), 2.11 d (3H, 6-CH3, J = 1.5 Hz), 7.02 q (1H,
2,5,6-Tribromo-4-[(4-bromophenyl)aminocar-
1
5-H, J3,5 = 0.9 Hz), 7.40 d (1H, 4′-H, J4′,6′ = 2.4 Hz),
7.60 q (1H, 3-H), 7.74 d (1H, 6′-H, J4′,6′ = 2.4 Hz),
8.96 br.s (1H, NH).
bonyloxyimino]cyclohex-2-en-1-one (IVc). H NMR
spectrum, δ, ppm: E isomer (30%): 4.84 d (1H, 6-H,
J5,6 = 2.7 Hz), 5.75 q (1H, 5-H, J3,5 = 1.2 Hz), 7.63 d
(1H, 3-H), 7.42–7.51 d.d (4H, C6H4, J = 8.7 Hz),
8.45 br.s (1H, NH); Z isomer (70%): 4.98 d (1H, 6-H,
J5, 6 = 3 Hz), 5.31 q (1H, 5-H), 7.42–7.51 d.d
(4H, C6H4, J = 8.7 Hz), 8.45 br.s (1H, NH), 8.15 d (1H,
3-H, J3,5 = 1.5 Hz).
2,6-Dimethyl-4-[(2,4,5-trichlorophenyl)amino-
carbonyloxyimino]cyclohexa-2,5-dien-1-one (XVIg).
4
1H NMR spectrum, δ, ppm: 2.10 d (3H, 2-CH3, J =
4
1.2 Hz), 2.11 d (3H, 6-CH3, J = 1.5 Hz), 7.02 q (1H,
5-H, J3,5 = 0.9 Hz), 7.52 s (1H, 3′-H), 7.60 q (1H,
3-H), 8.48 s (1H, 6′-H), 8.94 br.s (1H, NH).
2,5,6-Tribromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]cyclohex-2-en-1-one (IVf).
1H NMR spectrum, δ, ppm: E isomer (60%): 2.34 s
(3H, CH3C6H3), 4.86 d (1H, 6-H, J5,6 = 2.4 Hz), 5.78 q
(1H, 5-H), 7.17–7.19 d.d (1H, 5′-H, J5′,3′ = 1.8 Hz),
7.41 d (1H, 3′-H, J5′,3′ = 1.8 Hz), 7.61 d (1H, 3-H,
J3,5 = 1.8 Hz), 8.06 d (1H, 6′-H, J5′,6′ = 9 Hz), 8.55 br.s
(1H, NH); Z isomer (40%): 2.34 s (3H, CH3C6H3),
4.98 d (1H, 6-H, J5,6 = 2.7 Hz), 5.34 q (1H, 5-H),
7.17–7.19 d.d (1H, 5′-H, J5′,3′ = 1.8 Hz), 7.41 d (1H,
3′-H, J5′,3′ = 1.8 Hz), 8.06 d (1H, 6′-H, J5′,6′ = 8.1 Hz),
8.16 d (1H, 3-H, J3,5 = 0.9 Hz), 8.36 br.s (1H, NH).
4-[(4-Chlorophenyl)aminocarbonyloxyimino]-
2,6-diisopropylcyclohexa-2,5-dien-1-one (XVII).
Yield 88%, mp 101–102°C. H NMR spectrum, δ,
ppm: 1.16–1.18 d.d (12H, CH3, J = 1.8, 6.9 Hz), 3.06–
3.21 m (2H, 2-CH, 6-CH), 6.97 br.s (1H, 5-H), 7.35–
7.50 d.d (4H, C6H4, J = 8.1 Hz), 7.52 br.s (1H, 3-H),
8.87 br.s (1H, NH). Found, %: Cl 9.77, 9.90.
C19H21ClN2O3. Calculated, %: Cl 9.83.
1
2,6-Di-tert-butyl-4-[(2,4-dichlorophenyl)amino-
carbonyloxyimino]cyclohexa-2,5-dien-1-one
1
(XVIIIa). Yield 85%, mp 134–136°C. H NMR spec-
trum, δ, ppm: 1.32 d (18H, t-Bu, J = 1.8 Hz), 6.95 d
(1H, 5-H, J3,5 = 2.4 Hz), 7.30–7.34 d.d (1H, 5′-H,
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-2-methylcyclohex-2-en-1-one (Vb).
1H NMR spectrum, δ, ppm: E isomer (43%): 2.12 d
J5′,3′ = 2.1, J5′,6′ = 9 Hz), 7.44 d (1H, 3′-H, J5′,3′ = 2.1 Hz),
4
7.52 d (1H, 3-H, J3,5 = 2.4 Hz), 8.23 d (1H, 6′-H,
J5′,6′ = 9 Hz), 8.84 br.s (1H, NH). Found, %: Cl 16.71,
16.87. C21H24Cl2N2O3. Calculated, %: Cl 16.75.
(3H, 2-CH3, J = 1.2 Hz), 4.66 d (1H, 6-H, J5, 6
=
2.7 Hz), 5.72 q (1H, 5-H, J5,3 = 1.5 Hz), 6.95 q (1H,
3-H), 7.43–7.50 d.d (4H, C6H4, J = 8.7 Hz), 8.00 br.s
4
(1H, NH); Z isomer (57%): 2.12 d (3H, 2-CH3, J =
2,6-Di-tert-butyl-4-[(2-chloro-4-methylphenyl)-
1.2 Hz), 4.80 d (1H, 6-H, J5,6 = 3.3 Hz), 5.26 q (1H,
5-H, J5,3 = 1.5 Hz), 7.48 br.s (1H, 3-H), 7.43–7.50 d.d
(4H, C6H4, J = 8.7 Hz), 8.03 br.s (1H, NH).
aminocarbonyloxyimino]cyclohexa-2,5-dien-1-one
(XVIIIc). Yield 82%, mp 161–162°C. H NMR spec-
trum, δ, ppm: 1.32 s (18H, t-Bu), 2.33 s (3H,
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
841
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-2-methylcyclohex-2-en-1-
one (Vd). 1H NMR spectrum, δ, ppm: E isomer (82%):
en-1-one (VIIi). Yield 91%, mp 157–158°C. 1H NMR
spectrum, δ, ppm: 2.11 s (3H, 2-CH3), 2.29 s (3H,
3-CH3), 4.67 d (1H, 6-H, J5,6 = 2.4 Hz), 5.79 d (1H,
5-H), 7.30–7.32 d.d (1H, 4′-H, J4′,6′ = 2.7, J4′,3′ = 9 Hz),
7.60 d (1H, 3′-H), 7.71 d (1H, 6′-H), 8.01 br.s
(1H, NH). Found, %: Cl + Br 50.58, 50.67.
C15H12Br3ClN2O3. Calculated, %: Cl + Br 50.63.
4
2.13 d (3H, 2-CH3, J = 1.2 Hz), 2.33 s (3H,
CH3C6H3), 4.68 d (1H, 6-H, J5,6 = 2.7 Hz), 5.75 br.s
(1H, 5-H), 6.95 q (1H, 3-H, J5,3 = 1.5 Hz), 7.16–
7.19 d.d (1H, 5′-H, J5′,3′ = 1.8 Hz), 7.40 br.s (1H, 3′-H),
8.08 d (1H, 6′-H, J5′,6′ = 8.7 Hz), 8.63 br.s (1H, NH);
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-3,6-dimethylcyclohex-2-en-1-one (VIIIc).
Yield 71%, mp 182–183°C. 1H NMR spectrum, δ, ppm:
2.06 s (3H, 6-CH3), 2.31 br.s (3H, 3-CH3), 5.94 s (1H,
5-H), 6.33 br.s (1H, 2-H), 7.42–7.51 d.d (4H, C6H4, J =
9 Hz), 7.99 br.s (1H, NH). Found, %: Br 47.04, 47.16.
C15H13Br3N2O3. Calculated, %: Br 47.10.
4
Z isomer (18%): 2.13 d (3H, 2-CH3, J = 1.2 Hz),
2.33 s (3H, CH3C6H3), 4.81 d (1H, 6-H, J5,6 = 2.7 Hz),
5.28 q (1H, 5-H), 7.50 q (1H, 3-H, J5,3 = 1.5 Hz), 7.16–
7.19 d.d (1H, 5′-H, J5′,3′ = 1.8 Hz), 7.40 br.s (1H, 3′-H),
8.08 d (1H, 6′-H, J5′,6′ = 8.1 Hz), 8.54 br.s (1H, NH).
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-3-methylcyclohex-2-en-1-one (VIb). Yield
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-3,6-dimethylcyclohex-
2-en-1-one (VIIIe). Yield 77%, mp 123–124°C.
1H NMR spectrum, δ, ppm: 2.08 s (3H, 6-CH3),
2.34 br.s (3H, 3-CH3), 2.34 s (3H, CH3C6H3), 5.98 s
(1H, 5-H), 6.35 br.s (1H, 2-H), 7.17–7.20 d.d (1H, 5′-H,
J5′,3′ = 1.8 Hz), 7.41 br.s (1H, 3′-H), 8.16 d (1H, 6′-H,
J5′,6′ = 9 Hz), 8.98 br.s (1H, NH). Found, %: Br 45.77,
45.89. C16H15Br3N2O3. Calculated, %: Br 45.83.
1
93%, mp 163–165°C. H NMR spectrum, δ, ppm:
2.33 br.s (3H, 3-CH3), 4.61 q (1H, 6-H, J2,6 = 1.2 Hz),
5.80 d (1H, 5-H, J5,6 = 2.4 Hz), 6.31 br.s (1H, 2-H),
7.41–7.50 d.d (4H, C6H4, J = 9 Hz), 8.00 br.s (1H,
NH). Found, %: Br 48.38, 48.47. C14H11Br3N2O3. Cal-
culated, %: Br 48.43.
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-3-methylcyclohex-2-en-1-
one (VId). Yield 98%, mp 142–143°C. 1H NMR spec-
trum, δ, ppm: 2.34 s (3H, CH3C6H3), 2.36 br.s (3H,
3-CH3), 4.64 q (1H, 6-H, J2,6 = 1.5 Hz), 5.86 d (1H,
5-H, J5,6 = 2.7 Hz), 6.34 br.s (1H, 2-H), 7.18–7.21 d.d
(1H, 5′-H, J5′,3′ = 1.8 Hz), 7.41 br.s (1H, 3′-H), 8.15 d
(1H, 6′-H, J5′,6′ = 8.7 Hz), 8.92 br.s (1H, NH). Found,
%: Br 47.12, 47.16. C15H13Br3N2O3. Calculated, %:
Br 47.10.
5,6-Dibromo-4-[(2-bromo-5-chlorophenyl)-
aminocarbonyloxyimino]-3,6-dimethylcyclohex-2-
en-1-one (VIIIi). Yield 93%, mp 158–159°C. 1H NMR
spectrum, δ, ppm: 2.06 s (3H, 6-CH3), 2.31 d (1H,
3-CH3, 4J = 1.2 Hz), 5.92 s (1H, 5-H), 6.34 q (1H, 2-H,
4J = 1.2 Hz), 7.29–7.33 d.d (1H, 4′-H, J4′,6′ = 2.4,
J4′,3′ = 8.7 Hz), 7.60 d (1H, 3′-H), 7.71 d (1H, 6'-H),
8.05 br.s (1H, NH). Found, %: Cl + Br 50.54, 50.70.
C15H12Br3ClN2O3. Calculated, %: Cl + Br 50.63.
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-2,3-dimethylcyclohex-2-en-1-one (VIIc).
1
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-6-isopropyl-3-methylcyclohex-2-en-1-one
Yield 92%, mp 110–111°C. H NMR spectrum, δ,
ppm: 2.11 s (3H, 2-CH3), 2.29 s (3H, 3-CH3), 4.67 d
(1H, 6-H, J5,6 = 2.7 Hz), 5.82 d (1H, 5-H), 7.41–
7.50 d.d (4H, C6H4, J = 8.7 Hz), 7.95 br.s (1H, NH).
Found, %: Br 47.01, 47.13. C15H13Br3N2O3. Calculat-
ed, %: Br 47.10.
1
(IXb). H NMR spectrum, δ, ppm: 1.09–1.28 d.d [6H,
4
6-CH(CH3)2, J = 6.6 Hz), 2.27 d (3H, 3-CH3, J =
1.2 Hz), 2.30–2.40 m (1H, 6-CH), 5.83 s (1H, 5-H),
4
6.28 q (1H, 2-H, J = 1.2 Hz), 7.38–7.51 d.d (4H,
C6H4, J = 8.4 Hz), 8.02 br.s (1H, NH).
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-2,3-dimethylcyclohex-2-
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-2-isopropyl-5-methylcyclohex-2-en-1-one
1
en-1-one (VIIe). Yield 97%, mp 91–94°C. H NMR
1
(Xb). H NMR spectrum, δ, ppm: 1.15–1.22 d.d [6H,
spectrum, δ, ppm: 2.12 s (3H, 2-CH3), 2.33 s (3H,
2-CH(CH3)2, J = 6.9 Hz], 2.33 s (3H, 5-CH3), 3.05–
3.13 m (1H, 2-CH), 4.79 s (1H, 6-H), 7.43 br.s (1H,
2-H), 7.38–7.51 d.d (4H, C6H4, J = 8.4 Hz), 8.02 br.s
(1H, NH).
3-CH3), 2.33 s (3H, CH3C6H3), 4.69 d (1H, 6-H, J5,6
=
2.4 Hz), 5.86 d (1H, 5-H), 7.17–7.20 d.d (1H, 5′-H,
J5′,3′ = 1.8 Hz), 7.40 br.s (1H, 3′-H), 8.15 d (1H, 6′-H,
J5′,6′ = 9 Hz), 8.96 br.s (1H, NH). Found, %: Br 45.80,
45.92. C16H15Br3N2O3. Calculated, %: Br 45.83.
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-2-isopropyl-5-methyl-
5,6-Dibromo-4-[(2-bromo-5-chlorophenyl)-
aminocarbonyloxyimino]-2,3-dimethylcyclohex-2-
1
cyclohex-2-en-1-one (Xd). H NMR spectrum, δ,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

AVDEENKO et al.
842
1
ppm: 1.16–1.23 d.d [6H, 2-CH(CH3)2, J = 8.7 Hz],
2.33 s (3H, CH3C6H3), 2.36 s (3H, 5-CH3), 3.05–
3.16 m (1H, 2-CH), 4.79 s (1H, 6-H), 7.17–7.20 d.d
(1H, 5′-H, J5′,3′ = 1.8, J5′,6′ = 8.7 Hz), 7.41 br.s (1H,
(XIIIb). Yield 85%, mp 182–183°C. H NMR spec-
4
trum, δ, ppm: 2.08 d (3H, 2-CH3, J = 1.5 Hz),
2.33 br.s (3H, 5-CH3), 2.33 s (3H, CH3C6H3), 6.44 q
(1H, 6-H, J = 1.5 Hz), 7.17–7.20 d.d (1H, 5′-H, J5′,3′
4
=
3′-H), 7.56 br.s (1H, 3-H), 8.16 d (1H, 6′-H, J5′,6′
8.7 Hz), 8.96 br.s (1H, NH).
=
1.8, J5′,6′ = 9 Hz), 7.40 br.s (1H, 3′-H), 7.66 d (1H,
3-H), 8.16 d (1H, 6′-H, J5′,6′ = 9 Hz), 9.08 br.s (1H,
NH). Found, %: Br 21.91, 22, 10. C16H15BrN2O3. Cal-
culated, %: Br 22.00.
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-3-isopropyl-6-methylcyclohex-2-en-1-one
1
(XIc). Yield 82%, mp 91–92°C. H NMR spectrum,
4-[(2-Bromo-4-methylphenyl)aminocarbonyloxy-
imino]-2-isopropyl-5-methylcyclohexa-2,5-dien-1-
δ, ppm: 1.24–1.31 d.d [6H, 3-CH(CH3)2, J = 7.8 Hz],
2.05 s (3H, 6-CH3), 3.16–3.29 m (1H, 3-CH), 5.98 s
(1H, 5-H), 6.30 s (1H, 2-H), 7.42–7.51 d.d (4H, C6H4,
J = 8.7 Hz), 7.93 br.s (1H, NH). Found, %: Br 44.57,
44.70. C17H17Br3N2O3. Calculated, %: Br 44.64.
1
one (XIV). H NMR spectrum, δ, ppm: 1.16 d [6H,
2-CH(CH3)2, J = 8.4 Hz], 2.32 br.s (3H, 5-CH3), 2.33 s
(3H, CH3C6H3), 3.05–3.16 m (1H, 2-CH), 6.43 br.s
(1H, 6-H), 7.17–7.20 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′
=
5,6-Dibromo-3-isopropyl-6-methyl-4-[(4-methyl-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
one (XIe). H NMR spectrum, δ, ppm: 1.25–1.31 d.d
[6H, 3-CH(CH3)2, J = 6.9 Hz], 2.06 s (3H, 6-CH3),
2.35 s (3H, CH3C6H4), 3.20–3.30 m (1H, 3-CH), 6.03 s
(1H, 5-H), 6.29 s (1H, 2-H), 7.19–7.38 d.d (4H,
CH3C6H4, J = 7.8 Hz), 8.90 br.s (1H, NH).
8.7 Hz), 7.41 br.s (1H, 3′-H), 7.43 br.s (1H, 5-H),
8.16 d (1H, 6′-H, J5′,6′ = 8.7 Hz), 9.12 br.s (1H, NH).
1
4-[(4-Bromophenyl)aminocarbonyloxyimino]-
2,6-dimethylcyclohexa-2,5-dien-1-one (XVIc). Yield
1
77%, mp 149–150°C. H NMR spectrum, δ, ppm:
4
2.09 d (3H, 2-CH3, J = 1.8 Hz), 2.10 d (3H, 6-CH3,
4
4J = 1.5 Hz), 7.04 q (1H, 5-H, J = 1.5 Hz), 7.43–
5,6-Dibromo-4-[(2-bromo-4-methylphenyl)-
aminocarbonyloxyimino]-3-isopropyl-6-methyl-
7.55 d.d (4H, C6H4, J = 8.1 Hz), 7.62 q (1H, 3-H),
8.20 br.s (1H, NH). Found, %: Br 22.74, 22.93.
C15H13BrN2O3. Calculated, %: Br 22.88.
1
cyclohex-2-en-1-one (XIf). H NMR spectrum, δ,
ppm: 1.26–1.31 d.d [6H, 3-CH(CH3)2, J = 6.9 Hz],
2.07 s (3H, 6-CH3), 2.34 s (3H, CH3C6H3), 3.24–
3.36 m (1H, 3-CH), 6.00 s (1H, 5-H), 6.31 s (1H, 2-H),
7.17–7.20 d.d (1H, 5′-H, J5′,3′ = 1.8, J5′,6′ = 8.1 Hz),
7.40 br.s (1H, 3′-H), 8.16 d (1H, 6′-H, J5′,6′ = 8.1 Hz),
8.90 br.s (1H, NH).
4-[(4-Bromophenyl)aminocarbonyloxyimino]-
2,6-di-tert-butylcyclohexa-2,5-dien-1-one (XVIIIb).
1
Yield 86%, mp 172–174°C. H NMR spectrum, δ,
ppm: 1.31 s (18H, t-Bu), 6.97 d (1H, 5-H, J3,5
=
2.7 Hz), 7.45–7.51 d.d (4H, C6H4, J = 8.7 Hz), 7.51 br.s
(1H, 3-H), 8.23 br.s (1H, NH). Found, %: Br 18.32,
18.42. C21H25BrN2O3. Calculated, %: Br 18.44.
5,6-Dibromo-4-[(4-bromophenyl)aminocarbonyl-
oxyimino]-3,5-dimethylcyclohex-2-en-1-one (XIIb).
1H NMR spectrum, δ, ppm: E isomer (66%): 2.31 s
(3H, 5-CH3), 2.52 br.s (3H, 3-CH3), 4.72 d (1H, 6-H,
J2,6 = 1.2 Hz), 6.17 br.s (1H, 2-H), 7.39–7.49 d.d (4H,
C6H4, J = 9 Hz), 7.93 br.s (1H, NH); Z isomer (34%):
2.27 s (3H, 5-CH3), 2.60 s (3H, 3-CH3), 4.57 d (1H,
6-H, J2,6 = 1.5 Hz), 6.33 br.s (1H, 2-H), 7.39–7.49 d.d
(4H, C6H4, J = 9 Hz), 7.93 br.s (1H, NH).
4-[(2-Bromo-4-methylphenyl)aminocarbonyloxy-
imino]-2,6-di-tert-butylcyclohexa-2,5-dien-1-one
1
(XVIIId). Yield 93%, mp 150–152°C. H NMR spec-
trum, δ, ppm: 1.32 d (18H, t-Bu), 2.33 s (3H, CH3),
6.96 d (1H, 5-H, J3,5 = 2.4 Hz), 7.16–7.19 d.d (1H,
5′-H, J5′,3′ = 1.8, J5′,6′ = 8.7 Hz), 7.41 br.s (1H, 3′-H),
7.43 br.s (1H, 5-H), 7.54 br.s (1H, 3-H), 8.08 br.s (1H,
6′-H), 8.78 br.s (1H, NH). Found, %: Br 17.79, 17.94.
C22H27BrN2O3. Calculated, %: Br 17.86.
5,6-Dibromo-4-[(2-bromo-5-chlorophenyl)-
aminocarbonyloxyimino]-3,5-dimethylcyclohex-2-
en-1-one (XIIg). Yield 89%, mp 105–107°C. 1H NMR
spectrum, δ, ppm: 2.32 s (3H, 5-CH3), 2.52 br.s (3H,
3-CH3), 4.72 s (1H, 6-H), 6.18 br.s (1H, 2-H), 7.28–
7.31 d.d (1H, 4′-H, J4′,6′ = 2.4, J4′,3′ = 8.7 Hz), 7.60 d
(1H, 3′-H), 7.69 d (1H, 6′-H), 7.95 br.s (1H, NH).
Found, %: Cl + Br 50.57, 50.68. C15H12Br3ClN2O3.
Calculated, %: Cl + Br 50.63.
Bromination of 4-(arylaminocarbonyloxyimino)-
cyclohexa-2,5-dien-1-ones IIIg–IIIi in the presence
of LiCl (general procedure). A solution of 5 mmol of
compound IIIg–IIIi in 3 ml of acetic acid or chloro-
form was heated to the boiling point, 5 mmol of
lithium chloride was added in portions under stirring,
and a solution of 25 mmol of bromine in 2 ml of the
same solvent, heated to 50–60°C, was added dropwise
under vigorous stirring, the ratio compound III–bro-
4-[(2-Bromo-4-methylphenyl)aminocarbonyloxy-
imino]-2,5-dimethylcyclohexa-2,5-dien-1-one
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010

HALOGENATION OF N-SUBSTITUTED p-QUINONE MONOIMINES ... XI.
843
2. Avdeenko, A.P., Konovalova, S.A., Sergeeva, A.G.,
Zubatyuk, R.I., Palamarchuk, G.V., and Shishkin, O.V.,
Russ. J. Org. Chem., 2008, vol. 44, p. 1765.
3. Avdeenko, A.P., Konovalova, S.A., Sergeeva, A.G.,
Palamarchuk, G.V., and Shishkin, O.V., Russ. J. Org.
Chem., 2009, vol. 45, p. 674.
4. Tennant, J., Comprehensive Organic Chemistry,
Barton, D. and Ollis, W.D., Eds., Oxford: Pergamon,
1979, vol. 2. Translated under the title Obshchaya
organicheskaya khimiya, Moscow: Khimiya, 1982,
vol. 3, p. 639.
mine being 1:5. The mixture was heated for 5–10 min
under reflux with vigorous stirring. After cooling,
a crystalline solid precipitated and was filtered off and
recrystallized from benzene–hexane (1:1).
5-Bromo-4-[(4-bromophenyl)aminocarbonyloxy-
imino]-6-chloro-2,3-dimethylcyclohex-2-en-1-one
1
(XIXa). H NMR spectrum, δ, ppm: 2.11 s (3H,
2-CH3), 2.29 s (3H, 3-CH3), 4.55 d (1H, 6-H, J5,6
=
2.4 Hz), 5.80 d (1H, 5-H, J5,6 = 2.4 Hz), 7.42–7.50 d.d
(4H, C6H4, J = 6.9 Hz), 7.97 br.s (1H, NH).
5. Titov, E.A., Burmistrov, S.I., and Brazhnik, D.E.,
Zh. Obshch. Khim., 1963, vol. 33, p. 2270.
6. Titov, E.A. and Burmistrov, S.I., Ukr. Khim. Zh., 1960,
vol. 26, p. 744.
7. Titov, E.A. and Sukhina, N.K., USSR Inventor’s Certifi-
5-Bromo-6-chloro-2,3-dimethyl-4-[(4-methyl-
phenyl)aminocarbonyloxyimino]cyclohex-2-en-1-
one (XIXb). H NMR spectrum, δ, ppm: 2.13 s (3H,
1
2-CH3), 2.30 s (3H, 3-CH3), 2.34 s (3H, CH3C6H4),
4.53 d (1H, 6-H, J5,6 = 2.1 Hz), 5.81 d (1H, 5-H, J5,6
=
cate no. 255210 (1968), Byull. Izobret., 1969, no. 33.
2.1 Hz), 7.18–7.39 d.d (4H, CH3C6H4, J = 8.1 Hz),
7.97 br.s (1H, NH).
8. Avdeenko, A.P., Konovalova, S.A., Il’chenko, A.Ya.,
and Glinyanaya, N.M., Russ. J. Org. Chem., 2006,
vol. 42, p. 56.
5-Bromo-4-[(2-bromo-5-chlorophenyl)aminocar-
bonyloxyimino]-6-chloro-2,3-dimethylcyclohex-2-
9. Pirozhenko, V.V., Cand. Sci, (Chem.) Dissertation,
1
en-1-one (XIXc). H NMR spectrum, δ, ppm: 2.10 s
Kiev, 1992.
(3H, 2-CH3), 2.30 s (3H, 3-CH3), 4.56 d (1H, 6-H,
J5,6 = 2.7 Hz), 5.80 d (1H, 6-H, J5,6 = 2.7 Hz), 7.30–
7.33 d.d (1H, 4′-H, J4′,6′ = 2.4, J4′,3′ = 8.7 Hz), 7.60 d
(1H, 3′-H), 7.72 d (1H, 6′-H), 7.99 br.s (1H, NH).
10. Pirozhenko, V.V. and Avdeenko, A.P., Russ. J. Org.
Chem., 1995, vol. 31, p. 1514.
11. Avdeenko, A.P. and Glinyanaya, N.M., Russ. J. Org.
Chem., 1995, vol. 31, p. 1507.
12. Perrin, C.L. and Engler, R.E., J. Org. Chem., 1997,
vol. 62, p. 687.
REFERENCES
13. Avdeenko, A.P., Zhukova, S.A., Glinyanaya, N.M., and
Konovalova, S.A., Russ. J. Org. Chem., 1999, vol. 35,
p. 560.
1. Avdeenko, A.P., Konovalova, S.A., and Ludchenko, O.N.,
Russ. J. Org. Chem., 2009, vol. 45, p. 1799.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 6 2010