Activated sterically strained C=N bond in N-substituted p-quinone mono- and diimines: XIII. reactions of N-alkyl(aryl, trifl uoromethyl)sulfonyl-, N-arylsulfi nyl-and N-arylsulfanyl-1,4-benzoquinone monoimines with alcohols

Article abstract of DOI:10.1134/S107042801205003X

Steric strains arising between the substituent atoms at nitrogen (S, SO, or SO₂) and the methyl group located in positions 3 or 5 of the quinoid ring of 3,5-dimethyl-substituted quinone monoimines lead to the increased angle C=N-S. As a result in these quinone monoimines the reactions of 1,2-addition become thermodynamically possible since the formation of quinolide structures with the sp³-hybridized carbon atom removes the steric strain.

Full text of DOI:10.1134/S107042801205003X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 5, pp. 642−650. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, O.N. Mikhailichenko, A.A. Santalova, G.V. Palamarchuk, O.V. Shishkin, 2012, published in Zhurnal
Organicheskoi Khimii, 2012, Vol. 48, No. 5, pp. 647−654.
Activated Sterically Strained C=N bond in N-Substituted
p-Quinone Mono- and Diimines: XIII.* Reactions
of N-alkyl(aryl, trifluoromethyl)sulfonyl-, N-arylsulfinyl-
and N-arylsulfanyl-1,4-benzoquinone Monoimines with Alcohols
A. P. Avdeenkoa, S. A. Konovalovaa, O. N. Mikhailichenkoa, A. A. Santalovaa,
G. V. Palamarchukb, and O. V. Shishkinb,c
aDonbass State Engineering Academy, Kramatorsk, 84313, Ukraine
е-mail: chimist@dgma.donetsk.ua
bInstitute of single crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine
cKarazin Kharkov National University, Kharkov, Ukraine
Received December 8, 2011
Abstract—Steric strains arising between the substituent atoms at nitrogen (S, SO, or SO2) and the methyl group
located in positions 3 or 5 of the quinoid ring of 3,5-dimethyl-substituted quinone monoimines lead to the increased
angle С=N–S. As a result in these quinone monoimines the reactions of 1,2-addition become thermodynamically
possible since the formation of quinolide structures with the sp3-hybridized carbon atom removes the steric strain.
DOI: 10.1134/S107042801205003X
3,5-Disubstituted N-arylsulfonyl-1,4-quinone monoimines
enter the 1,2-addition reactions at the С=N bond with alcohols,
hydrazines, primary aromatic amines, dialkylphosphites, bis(p-
dimethylaminophenyl)phosphinite [2–9]. The С=N bond exhib-
its a higher reactivity due to the increased bond angle С=N–Х,
and its activity starts to appear at the angle С=N–Х exceeding
130 deg [3]. At the angle value over 145–150 deg the quinone
imines get thermodynamically unstable, and their synthesis
becomes impossible. These conclusions followed from the
study of the structural features of quinone imines on the pre-
cision 3D atomic-molecular models «Tartu Models» and also
from the XRD analysis of the 3,5-dimethyl-N-(4-chlorophenyl)
sulfonyl-1,4-benzoquinone monoimine (angle С=N–Х 132.7
deg) [3]. No XRD investigations of the other 3,5-disubstituted
1,4-quinone monoimines was performed.
The most studied among 1,2-addition reactions to
1,4-quinone monoimines are the reactions with alcohols
[2–5]. Yet as a result of the reaction with alcohols of
some 3,5-disubstituted N-arylsulfonyl-1,4-benzoquinone
monoimines having a bulky alkyl group (i-PrOH,
t-BuOH) previously mainly the hydrolysis products were
isolated, and in the case of N-arylsulfanylperchloro-
1,4-benzoquinone monoimines the initial quinone
monoimines were recovered [3]. The reactions with
alcohols of the other quinone imines containing a sulfur
atom linked to nitrogen were not examined.
The characteristic feature of 3,5-disubstituted
N-arylsulfonyl-1,4-benzoquinone monoimines is
the existence of a fast in the NMR time scale Z,E-
isomerization (topomerization) also due to the increased
angle С=N–Х as compared to the unsubstituted in the
quinone ring 1,4-benzoquinone monoimines [2, 5, 10].
The structural and spectral features of N-arylsulfanyl- and
N-arylsulfinyl-1,4-benzoquinone monoimine have not
been studied before.
The goal of this research was revealing the structural
features of 3,5-disubstituted 1,4-benzoquinone
monoimines containing sulfur atoms of diverse
oxidation state attached to the nitrogen atom, and
establishing the rules governing the reactions of these
quinone monoimines with alcohols. We selected as
objects of the study 3,5-dimethyl-(2,3,5,6-tetrachloro)-
substituted N-alkylsulfonyl- Iа–Ic, N-arylsulfonyl- Id–If,
N-trifluoromethylsulfonyl- (Ig), N-arylsulfinyl- IIа, IIb,
_______________
*For communication XII, see [1].
642

ACTIVATED STERICALLY STRAINED C=N BOND
643
and N-arylsulfanyl-1,4-benzoquinone monoimines IIIа,
IIIb.
In the IR spectra of compounds Vа–Vo the
characteristic absorption band of the С=О group of the
quinolide ring appears at 1690–1710 cm–1 in contrast to
the С=О group absorption in initial 1,4-benzoquinone
monoimines Iа–If (1635–1670 cm–1), and the absorption
band in the region 1545–1630 cm–1 corresponding to the
C=N group is absent.
The syntheses and spectra were previously described
for N-methyl(trifluoromethyl)sulfonyl- Iа, Ig [11],
N-arylsulfonyl- Id–If [7, 12], 3,5-dimethyl-N-aryl-
sulfanyl- IIIа, IIIb [Ar = Ph (а), Tol (b)] [13, 14]
1,4-benzoquinone monoimines. N-alkylsulfonyl- Ib, Ic
and N-arylsulfinyl derivatives IIа, IIb are prepared for
the first time.
1
In the Н NMR spectra of compounds Vа–Vo the
singlet of protons Н2,6 of the quinoid ring is observed
in the region 6.10–6.59 ppm, the signal of ОMе group
of compounds Vа–Vc, Vk, Vn, at 3.02–3.04 ppm as is
characteristic of quinolide structures [2–5], the signal of
the NH group appears in the region 4.90–6.51 ppm.
1
The Н NMR spectra of quinone monoimines Ib,
Ic, IIа, IIb similar to the spectra of formerly obtained
3,5-dimethyl derivatives Iа, Id, If, IIIа, IIIb [7, 11, 13]
contain the signals of protons Н2,6 as singlets in the region
6.37–6.58 ppm which shows the existence of the fast in
the NMR time scale Z,E-isomerization. In the 13С NMR
spectra of quinone imines IIа, IIb same as in the spectra
of quinone monoimines IIIа, IIIb [14], the nuclei of
atoms С3,5 and С2,6 are magnetically equivalent.
The rate of reaction of quinone imines Iа–If with
alcohols IVа–IVg depends on the volume of the
substituent at the sulfo group of quinone imines Iа–If
and of the alkyl group of the alcohols IVа–IVg. Thus
the reaction of N-alkylsulfonyl-1,4-benzoquinone
monoimines Iа–Ic with methanol (IVа) required 5–60
min, N-arylsulfonyl derivatives Id–If with alcohol IVd
took 24 h, and with alcohols IVe–IVg, up to 1 month.
Formerly the acceleration of the reaction with alcohols
was observed for N-{arylsulfonylimino[phenyl(methyl)]
methyl}-1,4-benzoquinone monoimines at replacement
of the phenyl substituent at the nitrogen for the methyl
group [15].
Formerly the reactions with alcohols were carried
out at boiling [2–5] which sometimes might provoke the
hydrolysis of initial quinone monoimine. In this study the
reactions were performed under mild conditions, at room
temperature. If the TLC monitoring showed that within
2 months the reaction failed to proceed, the reaction
mixture was subjected to boiling for 12 h.
As a result of reactions of quinone imines Iа–Ic with
methanol (IVа) and quinone imines Id–If with alcohols
IVа–IVg we obtained products of 1,2-addition: quinolide
structures Vа–Vo (Scheme 1). Compound Vd was
obtained for the first time; it could not be isolated before
due to the competing hydrolysis of quinone monoimine in
boiling alcohols [3]. We failed to obtain reaction products
of quinone imines Iа–Ic with alcohols IVb–IVg and
quinone imines Iа–If with t-BuOH IVh. The last reaction
is evidently impossible due to steric hindrances.
N-Trifluoromethylsulfonyl derivative Ig in the
presence of alcohols IVа–IVh at room temperature in
2 months hydrolyzed into the corresponding quinone VI
and trifluoromethanesulfonamide (VII) (Scheme 2). In
the 19F NMR spectrum the signal characteristic of quinone
imine Ig at –79.33 ppm disappeared, but appeared a
singlet at –79.85 ppm characteristic of amide VII [11].
Scheme 2.
Me
F3CSO2N
Me
H2O
CF SO NH
2
O
O
O
+
3
2
Scheme 1.
IVа–IVh
R2
R2
R1
R2
R1
AlkOH
Me
Ig
Me
IVа_IVg XSO2HN
VI
VII
O
XSO2N
O
AlkO
N-Aryl(alkyl)sulfonyl-1,4-benzoquinone monoimines
with unoccupied position 3 and/or 5 of the quinoid
ring do not react with alcohols. After the reaction of
N-trifluoromethylsulfonyl analogs with alcohols only the
corresponding quinones and trifluoromethanesulfonamide
were isolated from the reaction mixture, apparently due
to the low hydrolytic stability of the substrates [10].
R1
R2
R1
Iа_If
Vа_Vo
I, X = Me (а), Et (b), Pr (c), Ph (d), 4-MeС6Н4 (e, f); R1 = H,
R2 = Me (а–d, f), R1 = R2 = Cl (e); IV, Alk = Me (а), Et (b),
Pr (c), i-Pr (d), i-Bu (e), C5H11 (f), cyclo-C6H11 (g); V, X = Me
(а), Et (b), Pr (c), Ph (d–g), 4-MeС6Н4 (h–o); Alk = Me (а–c,
k, n), Et (l, o), Pr (m), i-Pr (d), t-Bu (e, h), C5H11 (f, i), cyclo-
C6H11 (g, j); R1 = H, R2 = Me (а–g, n, o), R1 = R2 = Cl (h–m).
In the reaction of N-arylsulfinyl-1,4-benzoquinone
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AVDEENKO et al.
644
Table 1. Some geometric parameters of N-substituted
1,4-benzoquinone monoimines Iа, Ih, Ii, IIb, IIc, IIIb, IIIc
according to XRD data
monoimines IIa, IIb with alcohols IVа–IVh also only
the products of the hydrolysis of the initial quinone imines
were obtained (Scheme 3).
Compound Angle С=N–S, Bond length Bond length
no.
deg
C=N, Å
N–S, Å
Scheme 3.
Iа
Ih
Ii
130.1
132.7
121.6
129.0
126.0
127.9
1.294
1.290
1.301
1.288
1.303
1.303
1.650
1.638
1.652
1.709
1.661
1.653
Me
O
O
H2O
ArSN
O
ArSNH2
+ VI
IVа–IVh
IIb
IIc
IIIb
Me
VIIIа, VIIIb
IIа, IIb
Ar = Ph (а), 4-MeОC6H4 (b).
IIIc
119.6
1.302
1.663
N-Arylsulfanyl derivatives IIIa, IIIb did not react
with alcohols IVа–IVh even at boiling for 12 h (the initial
reagents were recovered).
С7 2.955 (sum of the van der Waals radii 3.55 [17]), S1…
H7А 2.66 (3.00), S1… H7В 2.67 Å (3.00).
N-Arylsulfinyl derivatives IIb, IIc contain a chi-
ral sulfur(IV) atom with a lone electron pair, and the
group S=O may take different spatial positions with
respect to the quinoid ring as is actually observed in
quinone monoimines IIb, IIc. The S=O bond in both
quinone monoimines IIb, IIc deviates from the plane
of the quinoid ring: the torsion angle C4=N1–S1=O2 is
164.3(3) deg. However the group has different orientation
with respect to the S–N bond. In quinone monoimine IIc
this orientation is close to cisoid (torsion angle C4=N1–
S1=O2 –24.8(3) deg [16]), and in IIb, to transoid. Namely,
in the course of the synthesis that formed structure of the
molecule of 3,5-dimethyl-1,4-quinone monoimine IIb
is more favorable from the viewpoint of minimizing the
steric strains where the SO group is spatially removed
from the quinoid ring, and the intramolecular shortened
contacts exist only between atoms S1…С8 3.074 (3.55),
S1… H8С 2.77 (3.00), and S1… H8В 2.80 Е (3.00). On
the other hand, in 2,6-di-tert-butylquinone monoimine
IIc, unlike N-arylsulfanyl IIIc and N-arylsulfonyl Ii
derivatives the steric strain between the SO group and
the atoms of the С5–Н51 bond of the quinoid ring led to
the increase in the angle С4=N1–S1 to 126.0 deg, and
intramolecular shortened contacts are observed between
atoms О1…H51 2.25 (2.45 ), О1…С5 2.985 (3.00), S1…
H51 2.83 (3.00), S1…С5 3.154 Е (3.55) [16]. As a result
the angle С4=N1–S1 in 3,5-dimethyl derivative IIb com-
pared with 2,6-di-tert-butylquinone monoimine IIc is
increased only by 3 deg.
As known, the reactivity of quinone imines with respect
to alcohols depends on the value of the angle C=N–X
[2–5]. In order to establish the structural features of
N-methyl(trifluoromethyl)sulfonyl-, N-arylsulfinyl-, and
N-arylsulfanyl-1,4-benzoquinone imines and to compare
them with the previously studied 3,5-dimethyl-N-(4-
chlorophenyl)sulfonyl-1,4-benzoquinone monoimine (Ih)
we subjected to XRD analysis compounds Iа, IIb, IIIb
(Figs. 1–3). We failed to obtain crystals of compound Ig
because of its low stability in air.
Aiming at comparing the geometric parameters of
3
,5-dimethyl-substituted quinone imines containing
sulfur of diverse valence with analogous quinone imines
lacking substituents in the ortho-position to the nitrogen
atom we performed the XRD analysis on a single crystal
of 2,6-di-tert-butyl-N-arylsulfonyl derivative Ii (Fig. 4).
The XRD study of sulfinyl- and sulfanyl analogs IIc, IIIc
was carried out earlier [16].
In the series ArS (IIIb) → ArSO (IIb) → MeSO2
(Iа) →ArSO2 (Ih) [3] the value of the bond angle С=N–S
increased from 127.9(2) in quinone imine IIIb to 132.7(3)
deg in N-arylsulfonyl derivative Ih(Table1).
The molecule of 3,5-dimethyl-N-(4-tolyl)sulfanyl-
1,4-benzoquinone monoimine (IIIb) is virtually flat.
The angle С4=N1–S1 in this molecule is by 8.3deg larger
than in 2,6-di-tert-butyl derivative IIIc [16] but does not
exceed the value of 130 deg that was formerly suggested
as a criterion of the presence of a sterically strained С=N
bond [3]. The increased angle originates from the steric
strain between the sulfur atom and a methyl group in the
position 3 or 5 of the quinoid ring: the shortened intra-
molecular contacts are observed between the atoms S1…
The specific feature of quinone monoimines Iа, Ih, Ii
is the location of SO2 group symmetric with respect to the
plane of the quinoid ring. In this event in 3,5-dimethyl-
substituted quinone monoimines Iа, Ih a steric strain
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

ACTIVATED STERICALLY STRAINED C=N BOND
645
Fig. 3. Structure of 3,5-dimethyl-N-(4-tolyl)sulfanyl-1,4-
benzoquinone monoimine (IIIb) according to XRD data.
Fig. 1. Structure of N-mesyl-3,5-dimethyl-1,4-benzoquinone
monoimine (Iа) according to XRD data.
Fig. 4. Structure of 2,6-di-tert-butyl-N-(4-nitrophenyl)sulfonyl-
1,4-benzoquinone monoimine (Ii) according to XRD data.
Fig. 2. Structure of 3,5-dimethyl-N-(4-methoxyphenyl)sulfinyl-
1,4-benzoquinone monoimine (IIb) according to XRD data.
The introduction of substituents into the ortho-
position to the imine carbon atom results in a slight
decrease in the length of the N–S bond in N-arylsulfanyl
IIIb, IIIc and N-arylsulfonyl derivatives Ih, Ii. The
opposite trend is observed in N-arylsulfinylquinone
monoimines IIb, IIc: the length of the N–S bond in
3,5-dimethyl derivative IIb increased to 1.709 Å. With
increasing steric strain in the molecule in the series of
quinone imines IIIb–IIb–Iа the bonds С3–С4 and С4–
С5 regularly grow from 1.474(4) to 1.492(1) Å.
arises between the SO2 and methyl group in the position
3 or 5 of the quinoid ring which results in intramolecular
shortened contacts between atoms S1…С8 3.198 (3.55)
in quinone monoimine Iа and S1…С8 3.160 (3.55), О3…
H14А 2.37 (2.45), S1… H14А 2.73 A (3.00) in quinone
monoimine Ih and leads to the increase in the angle
С4=N1–S1 in 3,5-dimethyl-1,4-quinone monoimines Iа,
Ih. Consequently in these quinone monoimines contain-
ing a six-valent sulfur atom linked to the nitrogen the
maximum increase in the angle С4=N1–S1 is observed in
3,5-dimethyl derivative Ih amounting to 11.1 deg com-
pared to 2,6-di-tert-butylquinone monoimine Ii.
Thus the analysis of XRD data suggests a conclusion
that the increased angle С=N–S in 3,5-dimethyl-
substituted quinone monoimines IIIb, IIb, Iа, Ih
containing at the nitrogen atom an atom of two-, four,
and six-valent sulfur, as it has been concluded before,
originates from the steric strain arising between the
atoms of the substituent at the nitrogen (S, SO, or SO2)
and the methyl group in the position 3 or 5 of the quinoid
ring.
The length of the bond C=N in the quinone
monoimine series ArS → ArSO → ArSO2 does not
significantly change both in 2,6- and 3,5-disubstituted
derivatives. Yet it should be noted that the bond
lengths C=N in quinone monoimine IIIb and quinone
monoimines Ii, IIc, IIIc lacking the sterically strained
C=N bond at the nitrogen atom have close values
unlike quinone imines Iа, Ih, IIb where the C=N bond
is a little shorter (Table 1).
In order to rationalize the difference in the reactivity
of the considered quinone monoimines with respect
to alcohols we carried out ab initio quantum-chemical
calculations by the method B3LYP/6-31+G(d). The
energy of the ground state of compounds Iа, Id, Ig, Ij, Ik,
IIа, IIIа, Vа, Vp–Vw, IX obtained by quantum-chemical
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

AVDEENKO et al.
646
calculations and also the difference ΔЕtheor between
the energy of the end product (quinolide structure)
and the sum of the energies of initial substances [the
corresponding quinone monoimine and methanol, E(IVа)
–115.725193 a.u.] are presented in Table 2.
(IX), full agreement with experiment : These compounds
did not react with alcohols.
Quinone imine Ig in the reaction with alcohols IVa−
IVh suffered a hydrolysis even at the room temperature,
and quinone imine Iа was hydrolyzed at boiling with
alcohols IVb–IVh. In keeping with calculations the
energy difference between the final reaction product
Vu and the energy sum of the initial reagents Ig, IVа
was –1.72 kJ mol−1, and for compounds Vv and Iа, IVb
[E(IVb) –155.045511 a.u.] it was –1.94 kJ mol−1. We
presume that in these events beside the 1,2-addition of
the alcohol molecule a competing hydrolysis takes place
(1,2-addition–elimination) that becomes more favorable.
According to the calculated energy of quinolide
structures Vp, Vq which should form in the reaction of
unsubstituted and 2,6-dimethyl-N-phenylsulfonyl-1,4-
benzoquinone monoimines (Ij, Ik) with methanol IVа)
is larger than the sum of the energy of initial reagents
(ΔЕtheor 9.54 and 3.52 kJ mol−1 respectively). In the case
of 3,5-dimethyl-N-phenylsulfonyl-1,4-benzoquinone
monoimine (Id) the energy of the reaction product of
quinolide structure Vr is less than the sum of the energies
of the initial compounds Id, IVа (ΔЕtheor –7.39 kJ mol−1)
(Table 2). This fact shows that the reaction of 3,5-dimethyl-
N-phenylsulfonyl-1,4-benzoquinone monoimine (Id)
with methanol (IVа) is possible whereas the reactions
with methanol of unsubstituted and 2,6-dimethyl-1,4-
quinone monoimines (Ij, Ik) is impossible in total agree-
ment with the experimental results.
Proceeding from the quantum-chemical calculations
the reaction between N-arylsulfinyl-1,4-benzoquinone
monoimine IIа and methanol (IVа) should proceed
to give a quinolide structure Vw, for the energy of the
quinolide structure is less by 21.80 kJ mol−1 than the sum
of the energies of the initial compounds. Yet compounds
with vicinal SO and NH groups are unstable [18].
Therefore we presume that in this reaction first forms
quinolide structure Vw which subsequently undergoes
hydrolysis to compounds VI and VIIIа. This assumption
was also confirmed by the investigation of the process by
means of TLC: The formation of a product was detected
Higher theoretical energies of reaction products
Vs, Vt compared with the initial compounds were also
observed in quinone imine IIIa and its oxygen analog,
3,5-dimethyl-4- phenyloximinocyclohexa-2,5-dion-1-ene
Table 2. Total energy of reagents and reaction products according to quantum-chemical calculations
R1
R2
R1
AlkOH
IVа, IVb
R2
RHN
AlkO
R
N
O
O
R1
R1
R2
R2
Iа, Id, Ig, Ii, Ik
IIа, IIIа, IX
Vа, Vp–Vw
R
Еinit
,
а,b a.u.
Еend, a.u.
–1143.847282
ΔЕtheor, kJ mol−1
–2.83
MeSO2
MeSO2
CF3SO2
PhSO2
PhSO2
PhSO2
PhSO
PhS
Iа
Iа
–1028.121010
–1028.121010
–1325.836011
–1219.858931
–1219.871946
–1141.226485
–1144.644101
–1069.471307
–746.4719483
Vа
Vv
Vu
Vr
–1183.167259
–1441.56186
–1335.586936
–1335.593504
–1256.950338
–1260.377596
–1185.186553
–862.1786274
–1.94
Ig
1.72
Id
–7.39
Ij
Vp
Vq
Vw
Vs
9.54
Ik
3.52
IIа
IIIа
IX
–21.80
26.12
PhO
Vt
48.61
a Еinit = E(I−IX) + E(IV). bEnergy of alcohols: E(IVa) –115.725193; E(IVb) –155.045511 a.u.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

ACTIVATED STERICALLY STRAINED C=N BOND
647
whose Rf was the value close to Rf of quinolide structures.
work of the density functional theory applying functional
B3LYP [20–25]. The standard basis set 6-31+G(d) [26,
27] was used in the calculations. The XRD data were
taken as the initial parameters of the optimization. The
geometrical parameters of quinone imines Iа, Id, IIа,
IIIа after the optimization are well consistent with the
XRD data.
The analysis of the calculations data shows that from
the thermodynamical viewpoint the reaction with alcohols
is possible only for quinone monoimines with the CNS
angle exceeding 130 deg. The presence of substituents
in the positions 3 and 5 of the quinoid ring results in a
steric strain in the node C=N–S and, consequently, in
the activation of the C=N bond. Then the 1,2-addition
becomes thermodynamically probable since this removes
the steric strain: the С4 atom in the product is sp3-
hybridized.
IR spectra were taken on a spectrophotometer
Vertex-70 from solutions in CHCl3 (compounds Iа–Ig,
IIа, IIb, IIIа, IIIb, Vа–Vf, Vh, Vi, Vk–Vo) and in ace-
tone (compounds Vg, Vj). 1Н NMR spectra were recorded
on a spectrometer Varian VXR-300 (300 MHz) relative to
TMS in CDCl3 solution for compounds Ib, Ic, IIа, IIb,
Vа–Vf, Vh, Vi and in acetone-d6 for compounds Vg, Vj.
13С NMR spectra were recorded on a spectrometer Varian
VXR-300 (75.4 MHz) in CDCl3. The purity of quinone
imines and the products of their reactions was checked
EXPERIMENTAL
Quantum-chemical calculations were performed using
GAUSSIAN 03 software [19]. The molecular structure
of compounds under study was calculated in the frame-
Table 3. Main crystallographic parameters of quinone imines Iа, Ii, IIb, IIIb
Characteristics
Iа
Ii
IIb
IIIb
Unit cell parameters,
Å, deg
a 7.6940(5)
b 8.6599(7)
с 8.7955(6)
α 65.159(7)
β 72.246(6)
γ 74.865(7)
a 6.0953(14)
b 17.7251(19)
c 19.188(9)
β 91.14(3)
a 18.5040(7)
b 8.7800(2)
c 8.8490(3)
β 98.780(3)
a 13.5844(12)
b 11.8108(13)
c 16.8848(16)
V, Å3
500.46(6)
triclinic
Р-1
2072.7(11)
monoclinic
P21/c
4
1420.81(8)
monoclinic
P21/c
4
2709.0(5)
rhombic
Pbca
8
Crystal system
Space group
Z
2
F(000)
224
856
608
1088
1.262
0.226
50
D
calc g/cm3
1.415
0.304
60
1.296
0.189
50
1.353
0.234
50
μ(MoKα), mm–1
2θmax, deg
Reflections measured
Number of independent reflec-
tions
Rint
10253
2856
0.017
2317
130
8673
11009
2424
9073
2342
0.055
880
3598
0.026
2101
0.043
1586
Reflections with F > 4σ(F)
Number of parameters
259
181
166
wR2
0.085
0.030
1.017
848554
0.071
0.036
0.980
851690
0.155
0.053
1.011
848553
0.113
0.049
0.776
848552
R1 [F > 4σ(F)]
S
CCDC number
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

AVDEENKO et al.
648
benzoquinone monoimine (IIb). Yield 80%, mp
by TLC on Silufol UV-254 plates. Chloroform, acetone,
THF were used as solvents, eluents ethanol–chloroform,
1 : 10, benzene–hexane, 10:1, hexane–ethyl acetate, 1 :
2, development under UV radiation.
1
82–84°С. Н NMR spectrum, δ, ppm: 2.33 s (6H, 3,5-
Me), 3.87 s (3H, 4-MеОС6H4), 6.41 s (2Н, Н2,6), 7.04 d
(2Н, Н3',5', 4-MеOС6Н4, J 8.7 Hz), 7.77 d (2Н, Н2',6'
,
4-MеOС6Н4, J 8.7 Hz). 13С NMR spectrum, δ, ppm:
21.53 (3,5-Mе), 55.61 (MеО), 114.91 (С3',5'), 127.38
(С2',6'), 132.17 (С2,6), 137.39 (С1'), 146.23 (С3,5), 160.98
(C=N), 162.64 (С4'), 186.16 (C=О). Found, %: N 4.59,
4.83. C15H15NO3S. Calculated, %: N 4.84.
The XRD investigation of compounds Iа (C9H11NO3S,
M 213.25), IIb (C15H15NO3S, M 289.34), IIIb
(C15H15NOS, M 257.34), and Ii (C20H24N2O5S, M 404.47)
was carried out at 293K on an automatic four-circle dif-
fractometer Xcalibur 3 (MoKα, graphite monochromator,
CCD detector, ω-scanning). The structure was solved by
the direct method applying SHELXTLsoftware [28]. The
refinement was carried out in an anisotropic approxima-
tion for the nonhydrogen atoms. The position of hydro-
gen atoms were found from the difference synthesis of
the electron density and were refined in the rider model
with Uiso = nUeq of the nonhydrogen atom linked to this
hydrogen (n = 1.5 for methyl group, 1.2 for the other
hydrogen atoms) with a fixed parameter of the thermal
vibrations. The main crystallographic parameters are
given in Table 3. The final atomic coordinates, geometric
parameters of molecules and the crystallographic data are
deposited in the Cambridge Crystallographic Data Center
(e-mail: deposit@ccdc.cam.ac.uk).
Reactions of N-substituted 1,4-benzoquinone
imines Iа–Ig, IIа, IIb, IIIа, IIIb with alcohols IVа–IVh.
To a slurry of 1.4 mmol of benzoquinone monoimine Iа–
Ig, IIа, IIb, IIIа, IIIb in ethyl ether at room temperature
in a flow of argon was added 4 ml of anhydrous alcohol
IVа–IVh. The yellow color of the initial quinone imines
Iа–If gradually disappeared, and a colorless precipitate
separated of compounds Vа–Vo that were isolated and
washed with hexane or petroleum ether. The reactions of
quinone imines Iа–Ic with alcohols IVb–IVh, quinone
imines Ig, IIа, IIb with alcohols IVа–IVh, and quinone
imines Id–If with t-BuOH (IVh) were monitored by
TLC over 2 months, then the solvent was distilled off
in a vacuum to obtain the products of hydrolysis of ini-
tial quinone imines Iа–Ig. Mixtures of quinone imines
IIIа, IIIb and alcohols IVа–IVh were maintained over
2 months at room temperature without air access, then the
mixtures were boiled for 12 h and evaporated in a vacuum
to recover initial quinone imines IIIа, IIIb.
Quinone imines were synthesized by known proce-
dures: Iа–Ic, Ig [11], Id, If [7], Ie [12], IIа, IIb [29],
IIIа, IIIb [14]. The characteristics of compounds are
consistent with published data: Iа, Ig [11], Id, If [7], Ie
[12], IIIа, IIIb [13, 14], Vk–Vm [2], Vn, Vo [3].
N-(2,6-Dimethyl-1-methoxy-4-oxocyclohexa-2,5-
dien-1-yl)methanesulfonamide (Vа). Yield 78%, mp
172–173°С. Н NMR spectrum, δ, ppm: 2.07 s (6Н,
2,6-Mе), 2.99 s (3Н, MеSO2), 3.04 s (3Н, MеО), 5.28
br.s (1Н, NН), 6.31 s (2Н, Н3,5). Found, %: N 5.65, 5.87.
C10H15NO4S. Calculated, %: N 5.71.
3,5-Dimethyl-N-ethylsulfonyl-1,4-benzoquinone
monoimine (Ib). Yield 75%, mp 119–120°С. 1Н NMR
spectrum, δ, ppm: 1.52 t (3Н, СH2Me, J 7.8 Hz), 2.36 s
(6H, 3,5-Me), 3.34–3.41 m (2Н, СH2Me), 6.50 s (2Н,
Н2,6). Found, %: N 6.10, 6.29. C10H13NO3S. Calculated,
%: N 6.16.
1
N-(2,6-Dimethyl-4-oxo-1-ethoxycyclohexa-2,5-
dien-1-yl)methanesulfonamide (Vb). Yield 59%, mp
138–140°С. Н NMR spectrum, δ, ppm: 1.38 t (3Н,
СН2Mе, J 7.8 Hz), 2.07 s (6Н, 2,6-Mе), 2.99–3.07 m
(2Н, СН2Mе), 3.03 s (3Н, MеО), 5.19 br.s (1Н, NН),
6.30 s (2Н, Н3,5). Found, %: N 5.34, 5.55. C11H17NO4S.
Calculated, %: N 5.40.
3,5-Dimethyl-N-propylsulfonyl-1,4-benzoquinone
monoimine (Ic). Yield 61%, mp 91–93°С. 1Н NMR spec-
trum, δ, ppm: 1.10–3.36 m (7Н, Pr), 2.35 s (6H, 3,5-Me),
6.50 s (2Н, Н2,6). Found, %: N 5.65, 5.88. C11H15NO3S.
Calculated, %: N 5.80.
1
3,5-Dimethyl-N-phenylsulfinyl-1,4-benzoquinone
1
monoimine (IIа). Yield 82%, mp 79–81°С. Н NMR
spectrum, δ, ppm: 2.34 s (6H, 3,5-Me), 6.42 s (2Н, Н2,6),
7.55–7.83 m (5Н, Ph). 13С NMR spectrum, δ, ppm: 21.50
(3,5-Mе), 125.51 (С2',6'), 129.39 (С3',5'), 131.92 (С4'),
132.26 (С2,6), 145.95 (С1'), 146.22 (С3,5), 161.99 (C=N),
186.20 (C=О). Found, %: N 5.21, 5.45. C14H13NO2S.
Calculated, %: N 5.40.
N-(2,6-Dimethyl-4-oxo-1-propoxycyclo-hexa-2,5-
dien-1-yl)methanesulfonamide (Vc). Yield 45%, mp
106–109°С. Н NMR spectrum, δ, ppm: 1.02–3.00 m
(7Н, Pr), 2.06 s (6Н, 2,6-Mе), 3.02 s (3Н, MеО), 5.01 br.s
(1Н, NН), 6.30 s (2Н, Н3,5). Found, %: N 5.01, 5.20.
C12H19NO4S. Calculated, %: N 5.12.
1
N-[2,6-Dimethyl-4-oxo-1-(propan-2-yloxy)-
3,5-Dimethyl-N-(4-methoxyphenyl)sulfinyl-1,4-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

ACTIVATED STERICALLY STRAINED C=N BOND
649
J 8.2 Hz), 7.78 d (2Н, Н2',6', 4-MеС6Н4, J 8.2 Hz). Found,
%: N 2.80, 2.98. C19H19Cl4NO4S. Calculated, %: N 2.81.
cyclohexa-2,5-dien-1-yl]benzenesulfonamide (Vd).
Yield 66%, mp 122–123°С. 1Н NMR spectrum, δ, ppm:
1.08 d (6H, CHMe2, J 6.3 Hz), 1.76 s (6H, 2,6-Me),
3.52–3.60 m (1H, CHMe2), 5.53 br.s (1H, NH), 6.11 s
(2H, H3,5), 7.45–7.79 m (5H, Ph). Found, %: N 4.07, 4.21.
C17H21NO4S. Calculated, %: N 4.18.
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N-(1-tert-Butoxy-2,6-dimethyl-4-oxo-cyclohexa-
2,5-dien-1-yl)benzenesulfonamide (Ve). Yield 47%,
mp 135–137°С. 1Н NMR spectrum, δ, ppm: 0.88 d (6H,
СH2CHMe2, J 6.6 Hz), 1.72 s (6H, 2,6-Me), 1.72–1.82 m
(1H, CH2CHMe2), 2.74 d (2H, CH2CHMe2, J 6.6 Hz),
5.44 br.s (1H, NH), 6.11 s (2H, H3,5), 7.46–7.79 m (5H,
Ph). Found, %: N 3.95, 4.15. C18H23NO4S. Calculated,
%: N 4.01.
N-(2,6-Dimethyl-4-oxo-1-pentyloxycyclohexa-2,5-
dien-1-yl)benzenesulfonamide (Vf). Yield 45%, mp
1
109–111°С. Н NMR spectrum, δ, ppm: 0.85– 2.98 m
[11H, (СH2)4Me], 1.71 s (6H, 2,6-Me), 5.25 br.s (1H,
NH), 6.10 s (2H, H3,5), 7.45–7.76 m (5H, Ph). Found,
%: N 3.81, 4.06. C19H25NO4S. Calculated, %: N 3.85.
N-(2,6-Dimethyl-4-oxo-1-cyclohexyloxycyclohexa-
2,5-dien-1-yl)benzenesulfonamide (Vg). Yield 71%, mp
85–88°С. 1Н NMR spectrum, δ, ppm: 1.21–3.59 m (11H,
Cy), 1.93 s (6H, 2,6-Me), 6.50 s (1H, NH), 6.59 s (2H,
H3,5), 7.51–7.92 m (5H, Ph). Found, %: N 3.60, 3.76.
C20H25NO4S. Calculated, %: N 3.73.
12. Avdeenko, A.P., Velichko, N.V., Romanenko, E.A., Piro-
zhenko, V.V., and Shurpach, V.I., Russ. J. Org. Chem., 1991,
vol. 27, p. 2350.
13. Avdeenko, A.P., Konovalova, S.A., and Santalova, A.A.,
Vopr. Khim. Khim. Tekhnol., 2008, no. 1, p. 36.
14. Pirozhenko, V.V., Avdeenko, A.P., Yusina, A.L., and Kon-
ovalova, S.A., Russ. J. Org. Chem., 2004, vol. 40, p. 1121.
15. Avdeenko, A.P. and Marchenko, I.L., Russ. J. Org. Chem.,
2001, vol. 37, p. 1587.
16. Avdeenko,A.P., Pirozhenko, V.V., Konovalova, S.A., Santa-
lova, A.A., and Vakulenko, A.V., Arkivoc., 2005, vol. VIII,
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17. Zefirov, Yu.V. and Zorkii, P.M., Usp. Khim., 1989, vol. 58,
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N-(1-tert-Butoxy-4-oxo-2,3,5,6-tetrachloro-
cyclohexa-2,5-dien-1-yl)-toluene-4-sulfonamide
(Vh). Yield 84%, mp 177–179°С. 1Н NMR spectrum, δ,
ppm: 0.90 d (6H, СH2CHMe2, J 6.3 Hz), 1.81–1.91 m
(1H, CH2CHMe2), 2.44 s (3Н, 4-MeC6H4), 2.88 d (2H,
CH2CHMe2, J 6.3 Hz), 4.90 br.s (1H, NH), 7.32 d (2Н,
Н3',5', 4-MеС6Н4, J 7.8 Hz), 7.82 d (2Н, Н2',6', 4-MеС6Н4,
J 7.8 Hz). Found, %: N 2.75, 3.00. C17H17Cl4NO4S.
Calculated, %: N 2.96.
4-Methyl-N-(4-oxo-1-pentoxy-2,3,5,6-tetrachloro-
cyclohexa-2,5-dien-1-yl)benzenesulfonamide (Vi).
Yield 82%, mp 160–162°С. 1Н NMR spectrum, δ, ppm:
0.85–3.14 m [11H, (СH2)4Me], 2.44 s (3Н, 4-MeC6H4),
5.65 br.s (1H, NH), 7.28 d (2Н, Н3',5', 4-MеС6Н4,
J 8.8 Hz), 7.56 d (2Н, Н2',6', 4-MеС6Н4, J 8.8 Hz). Found,
%: N 2.70, 2.98. C18H19Cl4NO4S. Calculated, %: N 2.87.
18. Avdeenko, A.P., Konovalova, S.A., and Santalova, A.A.,
Russ. J. Org. Chem., 2007, vol. 43, p. 1471.
19. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E.,
Robb, M.A., Cheeseman, J.R., Montgomery, J.A.Jr.,
Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M.,
Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B.,
Cossi, M., Scalmani, G., Rega, N., Petersson, G.A.,
Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R.,
Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao,
4-Methyl-N-(4-oxo-2,3,5,6-tetrachloro-1-cyclo-
pentoxy-cyclohexa-2,5-dien-1-yl)benzene-sulfonamide
(Vj). Yield 48%, mp 109–110°С. 1Н NMR spectrum, δ,
ppm: 1.21–3.76 m (11H, Cy), 2.42 s (3Н, 4-MeC6H4),
6.51 br.s (1H, NH), 7.37 d (2Н, Н3',5', 4-MеС6Н4,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012

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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 5 2012