Reactions of N-arylsulfonyl-2-arenesulfonamido-1,4-benzo-quinone 4-imines with naphthols

Article abstract of DOI:10.1023/A:1015521918395

Reactions of N-arylsulfonyl-2-arenesulfonamido-1,4-benzoquinone 4-imines unsubstituted in the ring or 6-chloro and 5,6-dichlorosubstituted with 1- or 2-naphthols and 2-methoxynaphthalene provided the corresponding N-arylsulfonyl-2-arenesulfonamido-6-[2-hydroxy(methoxy)-1-naphthyl] -4-aminophenols from the unsubstituted reagent and reduction products from the mono- and dichlorosubstituted quinone imines.

Full text of DOI:10.1023/A:1015521918395

Russian Journal of Organic Chemistry, Vol. 38, No. 2, 2002, pp. 239 243. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 2, 2002,
pp. 260 264.
Original Russian Text Copyright
2002 by Avdeenko, Menafova, Evgafova.
Reactions of N-Arylsulfonyl-2-arenesulfonamido-1,4-
benzo-quinone 4-Imines with Naphthols
A. P. Avdeenko, Yu. V. Menafova, N. I. Evgrafova
Donbass State Machinebuilding Academy, Kramatorsk, 84313 Ukraine
Received November 22, 2000
Abstract Reactions of N-arylsulfonyl-2-arenesulfonamido-1,4-benzoquinone 4-imines unsubstituted in the
ring or 6-chloro and 5,6-dichlorosubstituted with 1- or 2-naphthols and 2-methoxynaphthalene provided the
corresponding N-arylsulfonyl-2-arenesulfonamido-6-[2-hydroxy(methoxy)-1-naphthyl]-4-aminophenols from
the unsubstituted reagent and reduction products from the mono- and dichlorosubstituted quinone imines.
Unlike reaction of N-substituted para-benzo-
quinone imines with phenols and naphthols in alkali-
water media (Burmistrov indophenol reaction [1]) that
affords indophenols(naphthols), the reaction between
N-substituted para-benzoquinone imines with phenols
and naphthols in organic solvents in the presence of
Lewis acids occurs as 1,4-addition yielding N-sub-
stituted 2-hydroxyaryl-4-aminophenols (naphthols).
Both the phenolate ion in the Burmistrov indo-
phenol reaction and the phenol molecule in the reac-
tion with N-substituted para-benzoquinone imines in
organic solvents in the presence of Lewis acids play
the role of a CH-acid.
The reaction of phenols and naphthols in the
presence of Lewis acid was in most detail investigated
by an example of N-arylsulfonyl-2-chloro-1,4-benzo-
(naphtho)quinone 4-imines [2 5]. It was demonstrated
2-Arenesulfonamido-N-arylsulfonyl-1,4-benzo-
quinone 4-imines can exist as two isomers (with
ortho- and para-quinoid structure with the latter of
lower redox potential prevailing). This fact affects the
that phenols addition occurred in the 4-position, that
direction of their reactions with different nucleo-
of 1-naphthols in 2-position, and of 2-naphthols in
philes. For instance, at HCl addition the Cl anion in
1-position [5]. The N-arylsulfonyl-2-chloro-1,4-benzo-
the first stage enters into 6-position, and in the second
quinone imines react with phenols and naphthols
stage into 5-position of the quinoid ring [7].
similarly to quinone imines unsubstituted in the
quinoid ring [4].
In reaction of N-arylsulfonyl-2,6-dichloro-1,4-
benzoquinone 4-imines with 2-naphthol occurs
nucleophilic substitution of one chlorine atom and
reduction of the arising quinoid product into 4-amino-
N-arylsulfonyl-6-(2-hydroxynaphthyl)-2-chlorophenols
[4].
The reaction with aromatic amines occurs as addi-
The methyl ethers of phenols and naphthols behave
tion of arylamino group to 5-position of the quinoid
with
N-arylsulfonyl-1,4-benzoquinone
imines
ring with simultaneous nucleophilic substitution of
the ArSO2 group adjacent to the imine nitrogen
followed by oxidation of the intermediate compound
with air oxygen to afford N-aryl-5-arylamino-2-
arenesulfonamido-1,4-benzoquinone-4-imines (B) as
final products [8].
analogously to the corresponding phenols and
naphthols [6].
The addition of phenols and naphthols in chloro-
form in the presence of BF3 apparently occurs via
intermediate formation of complex (A) [4].
1070-4280/01/3802-239$27.00 2002 MAIK Nauka/Interperiodica

240
AVDEENKO et al.
Scheme 1.
Ar = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c).
Scheme 2.
Ar = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c); X = H (II, VI), Cl (III, VII).
The other direction of reaction between N-aryl-
sulfonyl-2-arenesulfonamido-1, 4-benzoquinone
4-imines with naphthols also was not excluded.
In reaction with 2-naphthol N-arylsulfonyl-2-
arenesulfonamido-6-chloro-1, 4-benzoquinone
4-imines IIa c undergo reduction to the cor-
responding
chloro-4-arenesulfonamidophenols VIa c. Similar-
ly reacted N-arylsulfonyl-2-arenesulfonamido-
N-arylsulfonyl-2-arenesulfonamido-6-
The reaction with naphthols was studied on un-
substituted in the quinoid ring Ia c and also on
6-chloro IIa b, and 2,6-dichloro IIIa c derivatives
of N-arylsulfonyl-2-arenesulfonamido-1,4-benzo-
quinone imines.
5,6-dichloro-1,4-benzoquinone
(Scheme 2).
imines
IIIa c
In the study of the reaction between 2-naphthols
and substituted benzoquinone imines IIa c in one
case alongside the reduction was observed a nucleo-
philic substitution of a chlorine with 2-hydroxy-
naphthyl moiety with simultaneous reduction of the
intermediate quinone imine into compound IVa
identical to that obtained in reaction of quinone imine
Ia with 2 naphthol (Scheme 3).
Quinone imines Ia c react with 2-naphthol
similarly to unsubstituted in the ring N-aryl-
sulfonyl-1,4-benzoquinone imines, i.e. 2-naphthol
adds by 1,4 scheme to quinone imine with its active
1-position yielding 2,4-diarenesulfonamido-6-(2-
hydroxy-1-naphthyl)phenols IVa c (Scheme 1).
The reaction was carried out in chloroform in the
presence of catalytic amounts of boron trifluoride
etherate.
2-Methoxynaphthalene reacts with quinone imines
Ia c IIIa c similarly to 2-naphthol. With unsub-
stituted quinone imines Ia c occurs addition of
2-methoxynaphthalene to substrate along 1,4-scheme
at the active 1-position (Scheme 4) to yield com-
pounds VIIIa c.
We showed formerly [9] by an example of reaction
between N-arylsulfonyl-1,4-benzoquinone 4-imines
with phenols that on their oxidation with lead tetra-
acetate formed quinoneiminequinol acetates, and by
measuring the redox potentials of 4-arenesulfon-
amido-2-(2-hydroxy-1-naphthyl)phenols it was
demonstrated that the first stage consisted in forma-
tion of quinone imine and only in the second stage
arose quinoneiminequinol acetate [10]. The oxidation
of compounds IVa c with lead tetraacetate also
gave rise to N-arylsulfonyl-2-arenesulfonamido-6-(1-
acetoxy-1,2-dihydro-2-oxo-1-naphthyl)-1,4-benzo-
quinone 4-imines Va c (Scheme 1).
With mono- and dichloroquinone imines IIa c,
IIIa c we did not observe nucleophilic substitution
of chlorine, and in all cases, as with 2-naphthol, were
separated the corresponding reduced forms of quinone
imines VIa c, VIIa c.
Compounds VIIIa c on oxidation with lead
tetraacetate
afford
N-arylsulfonyl-2-arenesulfon-
amido-6-(2-methoxy-1-naphthyl)-1,4-benzoquinone
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002

REACTIONS OF N-ARYLSULFONYL-2-ARENESULFONAMIDO-1,4-BENZO-QUINONE 4-IMINES
241
Scheme 3.
Sceheme 4.
Ar = Ph (a), 4-µeC6H4 (b), 4-ClC6H4 (c).
4-imines IXa c. In the case 2-methoxy-1-naphthyl
fragment unlike 2-hydroxy-1-naphthyl moiety did not
suffer oxidation to quinol acetate.
In contrast to N-arylsulfonyl-1,4-benzoquinone
imines [5] quinone imines Ia c, IIa c, IIIa c are
reduced by 1-naphthol into the corresponding
N-arylsulfonyl-2-arenesulfonamido-4-amino-
phenols Xa c, VIa c, VIIa c. No hydroxyaryla-
tion was observed.
The structure of previously known compounds
arising in the course of reactions (VIa c, VIIa c and
2,4-diarenesulfonamidophenols Xa c) was confirmed
by comparison with authentic samples. In the IR
spectra of compounds Va c appear absorption band
in the range 3260 3250, 1755 1750, 1670 1660,
1645 1630, 1600 1590, 1340 1320 and 1180
1
1170 cm characteristic of groups NH, C=O, C=N,
and SO2 respectively.
1
The composition and structure of the newly syn-
thesized compounds are confirmed by elemental
analyses (Table 1) and 1H NMR spectra (Table 2).
The H NMR spectra of compounds IVb, c, Va,
c, VIIIa c are in total agreement with their assumed
structures.
Table 1. Yields, melting points, and elemental analyses of aminophenols IVa c, VIIIa c and of their oxidation products
Va c , IŒa c
Compd.
no.
mp, C (solvent
for crystallization)
Found S, %
Formula
Calculated S, %
Yield, %
IVa
IVb
IVc
Va
Vb
Vc
VIIIa
VIIIb
VIIIc
IXa
IXb
IXc
72
80
77
96
81
81
53
70
72
97
73
76
278 (C6H5NO2)
261 (CH3CO2H)
252 (CH3CO2H)
177 (decomp.) (toluene)
181 (decomp.) (CH3CO2H)
204 (decomp.) (toluene)
235 (CH3CO2H)
243 (CH3CO2H)
215 (CH3CO2H)
11.43, 11.72
10.78, 10.96
10.04, 10.23
10.72, 10.78
9.88, 10.02
9.61, 9.67
11.32, 11.67
11.74, 11.85
10.07, 10.21
11.45, 11.54
10.95, 10.98
10.10, 10.22
C28H23N2O6S2
C30H27N2O6S2
C28H21Cl2N2O6S2
C30H23N2O7S2
C34H26N2O7S2
C30H20Cl2N2O7S2
C29H24N2O6S2
C31H28N2O6S2
C29H22Cl2N2O6S2
C29H22N2O6S2
C31H26N2O6S2
C29H20Cl2N2O6S2
11.70
11.13
10.39
10.90
10.03
9.77
11.43
10.88
10.17
11.47
10.92
10.21
136 (decomp.) (CH3CO2H)
141 (decomp.) (CH3CO2H)
163 (decomp.) (CH3CO2H)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002

Table 2. Spectra 1H NMR (IVb, c, VIIIa c) and (Va, c)
Chemical shift, , ppm
ArSO2
Compd.
Solvent
H3
6.42 d
H5
H (naftalin)
NH, OH
CH3CO
CH3O
IVb
DMSO-d6
7.22 d
6.47-7.76 m (6H) 7.31-7.53 d.d (8H), 9.72 br.s (1H),
2.34 c (3H, CH3), 9.35 br.s (1H),
2.35 c (3H, CH3) 9.03 br.s (1H),
8.00 br.s (1H)
IVc
DMSO-d6
6.48 br.s
7.19 br.s 6.50-7.71 m (6H) 7.55-7.74 A-A (8H) 9.84 br.s (2H),
8.95 br.s (2H)
Va
Vc
CDCl3
Aceton-d6
7.88 d
7.76 d
7.36 d
7.32 d
6.33-8.08 m (6H) 6.33-8.08 m (10H) 8.88 br.s (1H) 2.02 c (3H)
6.22-8.12 m (6H) 7.47-7.79 d.d (4H), 9.30 m.c (1H) 2.04 c (3H)
7.64-7.79 d.d (4H)
VIIIa
VIIIb
VIIIc
DMSO-d6
DMSO-d6
DMSO-d6
6.40 d
6.39 d
6.40 d
7.25 d
7.24 d
7.19 d
6.47-7.92 m (6H) 7.20-7.65 m (10H) 9.83 br.s (1H),
9.17 br.s (1H),
3.65 c (3H)
3.66 c (3H)
3.67 c (3H)
8.13 br.s (1H)
6.50-7.94 m (6H) 7.32-7.54 d.d (8H), 9.79 br.s (1H),
2.35 c (6H, CH3) 9.12 br.s (1H),
8.14 br.s (1H)
6.46-7.94 m (6H) 7.60
7.65
c
c
(4H),
(4H)
9.94 br.s (1H),
9.37 br.s (1H),
8.22 br.s (1H)

REACTIONS OF N-ARYLSULFONYL-2-ARENESULFONAMIDO-1,4-BENZO-QUINONE 4-IMINES
243
EXPERIMENTAL
dissolution of the initial compounds. The solution
turned dark violet. To the cooled solution 2 ml of
ethylene glycol was added, the mixture was stirred
for 5 min, and left standing at room temperature for
several hours. The precipitate of dark-violet crystals
was filtered off and washed with methanol.
IR spectra were recorded on spectrophotometer
UR-20 from KBr pellets. 1H NMR spectra were
registered on Varian VXR-300 instrument at operat-
ing frequency 300 MHz with TMS as reference.
Initial quinone imines Ia c, IIa c, IIIa c were
prepared by oxidation with lead tetraacetate the cor-
Reaction of quinone imines IIa c, IIIa c with
2-naphthol or 2-methoxynaphthalene, and of
quinone imines Ia c, IIa c, IIIa c with 1-naphthol.
The reactions were carried out at the same conditions
as reactions of quinone imines Ia c with 2-naphthol
and 2-methoxynaphthalene. As a result we obtained
the corresponding reduced forms of quinone imines
Xa c, VIa c, VIIa c in 70 85% yield. The reaction
products were identified by comparison of the IR
spectra of compounds obtained with those of authentic
samples.
responding
2,4-diarenesulfonamidophenols
as
described in [78, 11].
N-Arylsulfonyl-2-arenesulfonamido-6-(2-hydr-
oxy-1-naphthyl)-4-aminophenols (IVa c). To
a
solution of 1 mmol of quinone imine Ia c in 5 ml
of chloroform was added 1,1mmol of 2-naphthol, the
mixture was heated to boiling, and 3 5 drops of
boron trifluoride etherate was added. Then the mix-
ture was left standing at room temperature for 24 h.
The separated precipitate was filtered off and washed
with a little of chloroform.
REFERENCES
Compound IVa was prepared also along the
above procedure from quinone imine IIa and double
excess of 2-naphthol. The compound was purified
from the reduction product by repeated recrystal-
lizations from acetic acid.
1. Avdeenko, A.P., Evgrafova, N.I., and Yusina, A.L.,
Vopr. Khim. i Khim. Tekhnol., Dnepropetrovsk, 2000,
no. 3, pp. 7 11.
2. Adams, R. and Eilar, K.R., J. Am. Chem. Soc.,
1951, vol. 73, no. 3, pp. 1149 1152.
3. Titov, E.A. and Podobuev, G.A., Zh. Org. Khim.,
1970, vol. 6, no. 3, pp. 544 549.
4. Podobuev, G.A., Cand. Sci. (Chem.) Dissertation,
Dnepropetrovsk, 1972.
5. Avdeenko, A.P., Zh. Org. Khim., 1989, vol. 25,
no. 11, pp. 2375 2381.
N-Arylsulfonyl-2-arenesulfonamido-6-(2-meth-
oxy-1-naphthyl)-4-aminophenols (VIIIa c) were
prepared analogously to compounds IVa c from
quinone imines Ia c and 2-methoxynaphthalene. The
characteristics of compounds VIIIa c are given in
Table 1.
6. Titov, E.A., Podobuev, G.A., and Prosyanik, A.V.,
Khim. Tekhnologiya, Khar,kov: Khar,kov. Gos.
Univ., no. 21, pp. 87 90.
7. Avdeenko, A.P., Evgrafova, N.I., Mishchenko A.I.,
and Belambri Nur Urida, Zh. Org. Khim., 1987,
vol. 23, no. 1, pp. 97 100.
N-Arylsulfonyl-2-arenesulfonamido-6-(1-acet-
oxy-1, 2-dihydro-2-oxo-1-naphthyl)-1,4-benzo-
quinone 4-imines (Va c). To a solution of 1 mmol of
aminophenol IVa c in 5 ml of acetic acid was added
2.2 mmol of lead tetraacetate, and the solution was
heated to boiling. As a result the solution turned
yellow. On cooling to room temperature 1 ml of
ethylene glycol was added, the mixture was stirred
for 5 min and was diluted with water. The separated
yellow precipitate was filtered off and washed with
methanol.
8. Avdeenko, A.P., Evgrafova, N.I., Tolmachev A.A.,
and Polyakov, A.E., Zh. Org. Khim., 1990, vol. 26,
no. 8, pp. 1751 1757.
9. Prikhod,ko, V.I., Avdeenko, A.P., Podobuev, G.A.,
Sharbatyan, P.A., and Budylin, V.A., Zh. Org. Khim.,
1974, vol. 10, no. 2, pp. 313 317.
10. Avdeenko, A.P., Burmistrov, K.S., and Evgrafo-
va N.I., Zh. Org. Khim., 1987, vol. 23, no. 9,
pp. 1935 1941.
11. Titov, E.A., Avdeenko, A.P., and Rudchenko V.F.,
Zh. Org. Khim., 1972, vol. 8, no. 12, pp. 2546 2549.
N-Arylsulfonyl-2-arenesulfonamido-6-(2-meth-
oxy-1-naphthyl)-1, 4-benzoquinone 4-imines
(IXa c). To a mixture of 10 mmol of aminophenol
VIIIa c in 10 ml of acetic acid was added 11 mmol
of lead tetraacetate, and the mixture was heated to
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002