Chlorination of N-acyl derivatives of p-aminophenols (naphthols) and p-phenylenediamines

Article abstract of DOI:10.1023/A:1012409614558

The chlorination of N-acyl derivatives of p-aminophenols can provide either N-acyl-2,3,6-trichloro-4-aminophenols or N-acyl-2,3,5,6-tetrachloro-1,4-benzoquinone imines depending on solvent nature, process temperature, and molar ratio initial compound-chlorine. The chlorination of N-acyl-4-amino-1-naphthols affords only N-acyl-2,3-dichloro-1,4-naphthoquinone imines. N,N′-Diacyl-1,4-phenylenediamines give rise on chlorination to a mixture of 2,5-dichloro-, 2,6-dichloro-, and 2,3-dichloro-N,N′-diacyl-1, 4-phenylenediamines.

Full text of DOI:10.1023/A:1012409614558

Russian Journal of Organic Chemistry, Vol. 37, No. 6, 2001, pp. 822 829. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 6, 2001,
pp. 869 876.
Original Russian Text Copyright
2001 Avdeenko, Marchenko.
Chlorination of N-acyl Derivatives of p-Aminophenols
(Naphthols) and p-Phenylenediamines
A. P. Avdeenko and I. L. Marchenko
Donbass State Macinebuilding Academy, Kramatorsk, 184313 Ukraine
Received November 5, 1999
Abstract The chlorination of N-acyl derivatives of p-aminophenols can provide either N-acyl-2,3,6-tri-
chloro-4-aminophenols or N-acyl-2,3,5,6-tetrachloro-1,4-benzoquinone imines depending on solvent nature,
process temperature, and molar ratio initial compound chlorine. The chlorination of N-acyl-4-amino-1-
naphthols affords only N-acyl-2,3-dichloro-1,4-naphthoquinone imines. N,N -Diacyl-1,4-phenylenediamines
give rise on chlorination to a mixture of 2,5-dichloro-, 2,6-dichloro-, and 2,3-dichloro-N,N -diacyl-1,4-
phenylenediamines.
N-Acetyl-4-aminophenol (Paracetamol) is an
efficient analgetic. Its oxidation product, N-acetyl-
1,4-benzoquinone imine is an intermediate in the
transformations sequence ensuring low toxicity of the
Paracetamol [1]. Therefore the investigation of N-acyl
derivatives of p-aminophenol (naphthol) and p-phenyl-
enediamine, and of their oxidation products, the
corresponding quinone imines, is of obvious interest.
The chlorination of N-acyl-4-aminophenols was
performed with the use of chlorine gas. We used as
solvents acetic acid, DMF, a mixture acetic acid
DMF (5: 1), chloroform, and tetrachloromethane.
Disregarding the character of solvent unlike the
chlorination of N-arylsulfonyl-4-aminophenols [4] the
first products isolated from the reaction mixture after
treating N-acetyl(aroyl)-4-aminophenols (Ia e) with
chlorine
were
N-acetyl(aroyl)-2,3,6-trichloro-4-
It was reported [1] that depending on reaction
conditions the chlorination of N-acetyl-4-aminophenol
gave rise to N-acetyl-2,3,5,6-tetrachloro-4-amino-
phenol or to N-acetyl-2,3,5,6-tetrachloro-1,4-benzo-
quinone imine. The chlorination of N,N -di-p-toluoyl-
1,4-phenylenediamine [2] was presumed to afford
N,N -di-p-toluoyl-2,5-dichloro-1,4-phenylenediamine;
yet the location of chlorine atoms in the molecule was
not proved.
aminophenols (IIa e) (Scheme 1).
On decreasing the ratio aminophenol chlorine we
failed to obtain the chlorination products containing
one or two chlorine atoms in the molecule: just was
reduced the yield of the trichloro derivatives IIa e,
or the chlorination failed to occur, and the initial
compounds were recovered.
Compounds IIa e of the highest purity were
obtained at chlorination in the acetic acid or its mix-
ture with DMF (5: 1).
The successive hydrochlorination and oxidation of
N,N -dibenzoyl-1,4-benzoquinone diimine is known
to provide as final product N,N -dibenzoyl-2,3,5-tri-
chloro-1,4-benzoquinone diimine [3]. The N,N -di-
benzoyl-2,3,5,6-tetrachloro-1,4-benzoquinone di-
imine was prepared starting with 2,3,5,6-tetrachloro-
1,4-phenylenediamine [3].
In DMF occurred deeper chlorination. In all cases
at certain ratios initial compound chlorine were
obtained
N-acetyl(aroyl)-2,3,5,6-tetrachloro-1,4-
benzoquinone imines (IVa e). The chlorination of
N-acetyl-4-aminophenol in DMF at the ratio amino-
phenol Cl2 1: 4 afforded N-acetyl-2,3,5,6-tetra-
chloro-4-aminophenol (IIIa) in agreement with the
published data [1].
In systematic investigation of chlorination of
N-arylsulfonyl derivatives of 1,4-benzo(naphtho)-
quinone monoimines and diimines and the reduced
forms thereof we obtained numerous chlorinated
derivatives of the above compounds depending on the
reaction conditions [4 7]. Therefore in the present
study we concentrated on chlorination of N-acyl
derivatives of p-aminophenols(naphthols) and
p-phenylenediamines.
The chlorination of compounds IIa e, IIIa in
DMF furnished N-acetyl(aroyl)-2,3,5,6-tetrachloro-
1,4-benzoquinone imines IVa e. Our attempt to
attain deeper chlorination of N-acetyl-4-aminophenols
in order to prepare semiquinoid substances similar to
those obtained at chlorination of N-arylsulfonyl-4-
1070-4280/01/3706-0822$25.00 2001 MAIK Nauka/Interperiodica

CHLORINATION OF N-ACYL DERIVATIVES OF p-AMINOPHENOLS
823
Scheme 1.
R = CH3 (a), C6H5 (b), 4-CH3C6H4 (c), 3-CH3C6H4 (d), 4-ClC6H4 (e).
aminophenols [4] by increasing the ratio of chlorine
to the initial compound was unsuccessful: In all runs
we isolated only chloranil (V) from the reaction
mixture. At longer reaction time and higher tempera-
ture alongside the main chlorination products a
hydrolysis product, chloranil (V), appeared in the
reaction mixture due to the side reaction with the air
moisture. In the tetrachloromethane N-acyl-4-amino-
phenols Ia e did not undergo chlorination.
(Table 2), and in the 13C NMR spectra of compounds
IVb, c, e appears the complete set of signals cor-
responding to these structures (Table 3).
The chlorination of N-acyl-4-amino-1-naphthols
VIa d was also performed with the use of chlorine
gas. DMF was used as a solvent. N-Acyl-4-amino-1-
naphthols VIa d in any solvent, notwithstanding
the molar ratio initial compound chlorine and
temperature, are chlorinated into N-acyl-2,3-dichloro-
1,4-naphthoquinone imines (VIIa e) (Scheme 2).
The composition and structure of compounds
IIa e, IIIa, IVa e were proved by elemental
N-Aroyl-2,3-dichloro-1,4-naphthoquinone imines
VIIb e were stable against hydrolysis: No hydro-
lysis product, 2,3-dichloro-1,4-naphthoquinone was
detected in the reaction mixture at the process carried
out at higher temperature and at higher excess of
chlorine. The hydrolysis product was found in the
reaction mixture by TLC method at chlorination of
N-acetyl-4-amino-1-naphthol (VIa).
1
analysis, IR, H and 13C NMR spectra.
In the IR spectra of compounds IIb e are present
absorption bands in the regions 3400 3250, 3330
1
3200, 1650 1630 cm , characteristic of groups OH,
NH, and C=O respectively, and in the IR spectra of
compounds IVb e in the regions 1690 1675, 1645
1
1640, 1600 1590 cm , characteristic of groups C=O
(quinoid), C=O (aroyl), and C=N respectively.
The reduced amount of chlorine with respect to
the initial substance did not result in formation of
chlorination products containing a single chlorine
atom (either in oxidized or reduced form) or a
chlorinated reduced form with two chlorine atoms,
only decreased the yield of compounds VII. At the
1
In the H NMR spectra of compounds IIa c appear
a proton singlet from H5 in 7.58 7.65 range and
the proton signals from groups R CO, NH, and OH.
1
In the H NMR spectra of compounds IVb, c, e are
observed signals from protons of R CO groups
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

824
AVDEENKO, MARCHENKO
Table 1. Melting points and elemental analyses of compounds Ic e, IIa e, IVb e, VIc d, VIIa e,VIIId, e, IXa
Found, %
Calculated, %
Compd.
no.
mp,
oC
Formula
Cl
N
Cl
N
Ic
Id
Ie
IIa
IIb
IIc
IId
IIe
IVb
IVc
IVd
IVe
VIc
VId
VIe
VIIa
VIIb
VIIc
VIId
VIIe
VIIId
VIIIe
IXa
207
155
250
195
182
178
208
203
225
233
170
215
230
250
265
5.83, 5.97
5.86, 6.01
5.34, 5.43
C14H13NO2
C14H13NO2
6.17
6.17
5.66
C13H10ClNO2
C8H6Cl3NO2
C13H8Cl3NO2
C14H10Cl3NO2
C14H10Cl3NO2
C13H7Cl4NO2
C13H5Cl4NO2
C14H7Cl4NO2
C14H7Cl4NO2
C13H4Cl5NO2
C18H15NO2
41.53, 41.68
33.20, 33.37
31.86, 31.99
31.72, 31.88
39.93, 39.97
40.07, 40.28
39.02, 39.23
38.67, 38.72
45.74, 45.85
41.79
33.59
32.17
32.17
40.39
40.63
39.06
39.06
46.23
4.58, 4.73
4.48, 4.70
13.65, 13.82
5.02
4.71
13.77
C17H12ClNO2
C17H11N3O6
245 (decomp.)
152
26.03, 26.38
21.51, 21.67
20.60, 20.92
28.74, 29.06
16.45, 16.71
C12H7Cl2NO2
C17H9Cl2NO2
C18H11Cl2NO2
C17H8Cl3NO2
C17H7Cl2N3O6
C22H20N2O2
26.45
21.52
20.65
29.10
16.88
188
210
142
300
360
295
8.07, 8.19
7.08, 7.13
8.13
7.28
C20H14Cl2N2O2
C10H10Cl2N2O2
26.71, 26.94
27.18
ratio N-aroyl-4-amino-1-naphthol chlorine equal to
1: 1 no chlorination occurred.
The composition and structure of compounds VII
were proved by elemental analysis, IR, 1H and
13C NMR spectra. In the IR spectra of compounds
VIIa e appear absorption bands in the regions
The chlorination of N-acyl-4-amino-1-naphthols to
only 2,6-dichloro-1,4-naphthoquinone imines whereas
the N-acyl-4-aminophenols predominantly afford the
chlorinated products of the reduced form is due to
lower redox potentials of the N-substituted
1,4-naphthoquinone imines as compared with those
of N-substituted 1,4-benzoquinone imines [8].
1
1680 1660, 1645 1630, 1590 1585 cm character-
istic of groups C=O (quinoid), C=O (acyl), and
1
C=N respectively. In the H NMR spectra of com-
pounds VIIa c are present signals from four protons
attached to the naphthalene skeleton and the proton
signals from the R CO groups (Table 2). In the
13C NMR spectrum of compound VIIb appears a
complete set of signals corresponding to its structure
(Table 3).
Scheme 2.
The chlorination of N,N -diacyl-1,4-phenylenedi-
amines VIIIa e was carried out in DMF or its mix-
ture with acetic acid (1: 5) with chlorine gas. The
chlorination of N,N -diaroyl-1,4-phenylenediamines
VIIIb e yields a mixture of three isomers: N,N -di-
aroyl-2,5-dichloro-1,4-phenylenediamines
N,N -diaroyl-2,6-dichloro-1,4-phenylenediamines
IXb e,
R = CH3 (a), C6H5 (b), 4-CH3C6H4 (c), 4-ClC6H4
(d), 2,4-(NO2)2C6H3 (e).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

1
Table 2. H NMR Spectra of compounds IIa c, IIIa, IVb, c, e, VIIa c, IXa c, Xb, c, XIb, c, XIIb e, XIIIb e, XIVb e, XV, XVI
Compd. no.
(contents in
mixture, %)
Chemical shift, , ppm
RCO protons
Solvent
Nuclea protons
NH
OH
10.06 s
10.35 s
10.05 s
10.55 s
IIa
IIb
IIc
IIIa
IVb
IVc
IVe
VIIa
DMSO-d6 7.65 s (1H, H5)
2.09 s (3H, CH3)
7.49 7.99 m (5H)
9.32 s
9.89 s
DMSO-d6 7.58 s (1H, H5)
DMSO-d6 7.61 s (1H, H5)
7.33 7.89 d.d (4H), 2.38 s (3H, CH3) 9.87 s
DMSO-d6
CDCl3
CDCl3
2.11 s (3H, CH3)
7.49 7.83 m (5H)
9.93 s
7.29 7.72 d.d (4H), 2.44 (3H, CH3)
7.47 7.78 d.d (4H)
CDCl3
CDCl3
CDCl3
CDCl3
8.27 q (1H, H5), 8.16 q (1H, H8), 1.62 s (3H, CH3)
7.83 7.86 m (2H, H6, H7)
VIIb
VIIc
8.26 q (1H, H5), 8.22 q (1H, H8), 7.47 7.91 (5H)
7.73 7.76 m (2H, H6, H7)
8.25 q (1H, H5), 8.20 q (1H, H8), 7.28 7.80 d.d (4H), 2.44 s (3H, CH3)
7.72 7.76 m (2H, H6, H7)
IXa
IXb (20)
Xb (75)
DMSO-d6 7.89 s (2H, H3, H6)
DMSO-d6 7.86 s (2H, H3, H6)
DMSO-d6 8.06 s (2H, H3, H5)
2.10 s (6H, CH3)
7.51 8.02 m (10H)
7.51 8.02 m 10H)
9.58 br.s (2H)
10.11 br.s (2H)
10.24 s 1H),
10.56 s (1H)
10.23 br.s (2H)
7.46 8.15 d.d (8H), 2.44 s (6H, CH3) 10.02 br.s (2H)
7.37 7.95 d.d (8H), 2.41 s (6H, CH3) 10.47 br.s (2H)
7.34 7.95 d.d (8H), 2.45 s (6H, CH3) 10.33 br.s (2H)
7.49 7.95 m (10H)
XIb (5)
IXc (30)
Xc (60)
DMSO-d6 7.76 s (2H, H3, H6)
DMSO-d6 7.85 s (2H, H3, H6)
DMSO-d6 7.97 s (2H, H3, H5)
DMSO-d6 7.62 s (2H, H5, H6)
7.51 8.02 m (10H)
Xlc (10)
XIIb (38)
XIIIb (55)
XIVb (7)
XIIc (20)
XIIIc (77)
XIVc (3)
XIId (79)
XIIId (16)
XlVd (5)
XIIe (67)
XIIIe (6)
XIVe (27)
XV
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
CDCl3
7.09 s (2H, H3, H6)
7.16 s (2H, H3, H5)
6.74 s (2H, H5, H6)
6.89 s (2H, H3, H6)
7.12 s (2H, H3, H5)
6.83 s (2H, H5, H6)
6.91 s (2H, H3, H6)
7.13 s (2H, H3, H5)
6.72 s (2H, H5, H6)
6.93 s (2H, H3, H6)
7.11 s (2H, H3, H5)
6.76 s (2H, H5, H6)
6.92 s (4H, H2, H3, H5,H6)
7.49 7.83 m (5H), 7.49 7.95 m (5H)
7.46 7.91 m (10H)
7.30 7.83 d.d (8H), 2.43 s (6H, CH3)
7.30 7.83 d.d (8H), 2.45 s (6H, CH3)
7.30 7.83 d.d (8H), 2.46 s (6H, CH3)
7.34 7.73 m (8H), 2.41 s (6H, CH3)
7.34 7.73 m (8H), 2.43 s (6H, CH3)
7.34 7.73 m (8H), 2.47 s (6H, CH3)
7.45 7.88 d.d (8H)
7.45 7.88 d.d (8H)
7.45 7.88 d.d (8H)
7.46 7.93 m (10H)
XVI
7.23 s (1H, H33), 6.83 s (2H, H5, H6) 7.47 7.93 m (10H)

826
AVDEENKO, MARCHENKO
Table 3. 13C NMR spectra (CDCl3) of N-aroyl-2,3,5,6-tetrachloro-1,4-benzoquinone imines (IVb, c, d) and
N-benzoyl-2,3-dichloro-1,4-naphthoquinone imine (VIIb)
Compd.
Chemical shift, C, ppm
no.
IVb
IVc
174.81 (C=O aroyl), 169.45 (C=O), 142.97 (C=N), 139.39 (C3, C5), 138.55 (C2, C6), 133.94 (C4 in
ArCO), 131.71 (C1 in ArCO), 129.01 (C3 in ArCO), 128.80 (C2 in ArCO)
174.79 (C=O aroyl), 169.48 (C=O), 144.99 (C=N), 142.80 (C4 in ArCO), 139.48 (C3, C5), 138.46
(C2, C6), 129.73 (C3 in ArCO), 129.04 (C1 in ArCO), 128.86 (C2 in ArCO), 21.79 (CH3 in ArCO)
IVe
173.72 (C=O aroyl), 169.35 (C=O), 143.44 (C=N), 140.57 (C4 in ArCO), 139.23 (C3, C5), 138.78 (C2, C6),
131.10 (C1 in ArCO), 130.13 (C3 in ArCO), 129.46 (C2 in ArCO)
VIIb
176.13 (C=O aroyl), 175.71 (C=O), 146.60 (C=N), 141.55, 140.10 (C9, C10), 134.28, 132.91, 127.97,
127.64 (C5, C6, C7, C8), 133.47 (C4 in C6H5CO), 132.20, 131.49 (C2, C3), 130.36 (C1 in C6H5CO), 128.86,
128.79 (C2, C3 in C6H5CO)
Xb e, and N,N -diaroyl-2,3-dichloro-1,4-phenyl-
ene diamines XIb e (Scheme 3).
ation process includes a stage of the quinoid structure
formation; the increased number of chlorine atoms
attached to the p-phenylenediamine ring causes
growth of the redox potential, and further chlorin-
ation becomes impossible.
The content of isomers in the mixture was
1
evaluated from the integrated signals in the H NMR
spectra. The elemental analyses show that in the
isomer mixtures are no substances of another com-
position. A single isomer, N,N -diacetyl-2,5-di-
chloro-1,4-phenylenediamine (IXa) was obtained
from N,N -diacetyl-1,4-phenylenediamine (VIIIa).
This product was identic to a compound with the
known structure [9].
Since the chlorination of compounds VIIIb e gave
rise to a mixture of three isomers IX, X, XI that posed
1
a great problem to investigation by H NMR we
effected oxidation of these mixtures to the cor-
responding quinone diimines: N,N -diaroyl-2,5-di-
chloro-1,4-benzoquinone diimines XIIb e, N,N -
diaroyl-2, 6-dichloro-1,4-benzoquinone diimines
We did not observe deeper chlorination of the
N,N -diacyl-1,4-phenylenediamines. It is apparently
due to significantly higher redox potentials of the
p-benzoquinone diimines as compared to those of
p-benzoquinone monoimines [8]. Besides the chlorin-
XIIIb e,
N,N -diaroyl-2,3-dichloro-1,4-benzo-
quinone diimines XIVb e (Scheme 3). The
1H NMR spectra of the latter compounds are more
informative. In order to assign the proton signals of
Scheme 3.
R = CH3 (a), C6H5 (b), 4-CH3C6H4 (c), 3-CH3C6H4 (d), 4-ClC6H4 (e).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

CHLORINATION OF N-ACYL DERIVATIVES OF p-AMINOPHENOLS
827
the quinoid ring in the isomers we synthesized N,N -
dibenzoyl-1,4-benzoquinone diimine (XV) [3], N,N -
dibenzoyl-2-chloro-1,4-benzoquinone diimine (XVI)
[3], and N,N -dibenzoyl-2,6-dichloro-1,4-benzo-
quinone diimine (XIIIb) [3]. Their spectra are given
in Table 2.
Ia, b, VIa, b, VIIIa c are consistent with the
published data.
In the experiments were used recrystallized sub-
stances, dried and freshly distilled solvents.
N-Aroyl-1,4-aminophenols(naphthols)
Ic e,
VIc e, N,N -diaroyl-1,4-phenylenediamines
1
Due to the fast Z,E-isomerization (in the H NMR
VIIId, e. To a solution of 0.5 mol of p-amino-
phenol(naphthol) or p-phenylenediamine and 0.5 mol
of anhydrous sodium acetate in 0.5 l of DMF AcOH
mixture, 1: 3, were added at cooling while stirring by
small portions the appropriate acyl chlorides in
equimolar amounts. On completing the acyl chloride
addition the stirring was continued for 30 min. The
precipitate was filtered off, compounds Ic e, VIc e
were recrystallized from acetic acid, compounds
VIIId, e from DMF. The yields of compounds
obtained are as follows: 75% (Ic), 64% (Id), 68%
(Ie), 55% (VIc), 51% (VId), 58% (VIe), 67%
(VIIId), 62% (VIIIe). The melting points and
elemental analyses are given in Table 1.
time scale) of p-quinone imines N-aroyl derivatives
as we have established previously [10] all the protons
of the quinoid ring of compound XV appear in the
1H NMR spectrum as a singlet, the proton H4
neighboring to the chlorine in compound XVI gives a
singlet at 7.23 ppm, and to the protons H5, H6
belongs a common singlet at 6.83 ppm. The protons
H3, H5 of compound XIIIb also appear as one singlet
resonance at
7.16 ppm.
1
In the H NMR spectra of isomer mixtures XII,
XIII, XIV the signals of the quinoid ring protons
appear respectively in the 7.11 7.16 ppm region for
2,6-dichloro derivatives XIIIb e,
6.89 7.09 ppm
for 2,5-dichloro derivatives XIIb e, and 6.72 6.83
for 2,3-dichloro derivatives XIVb e. As show the
1H NMR spectra, in the mixture are usually prevail-
ing isomers XII or XIII. Compounds IX XIV were
not isolated as individual substances. The analysis of
the spectra of isomers XII, XIII, and XIV indicated
that the compound described in [2] as N,N -di-p-
toluoyl-2,5-dichloro-1,4-benzoquinone diimine (XIIc)
was really its isomer N,N -di-p-toluoyl-2,6-dichloro-
1,4-benzoquinone diimine (XIIIc). Thus the separated
in [2] chlorination product was not N,N -di-p-toluoyl-
2,5-dichloro-1,4-phenylenediamine (IXc) but N,N -
di-p-toluoyl-2,6-dichloro-1,4-phenylenediamine (Xc).
N-Aroyl(acetyl)-2,3,6-trichloro-4-aminophenols
(IIa e). Through a solution of 0.5 g of compound
Ia e in 3 ml of one of solvents DMF, CH3CO2H,
DMF CH3CO2H mixture, 1: 5, or CHCl3 was passed
1
chlorine gas at a rate 15 20 ml min till the addi-
tional weight of the mixture corresponded to the
desired molar ratio initial compound chlorine. (a)
Compounds IIa e were prepared by chlorination in
acetic acid in the temperature range 20 45 C at molar
ratio initial compound chlorine in the 1: 2 to 1: 6
range. The best yield and purity of compounds IIa e
were obtained at the ratio initial compound chlorine
1: 4 and 30 40 C. Yields of the reaction products
were as follows: IIa 89%, IIb, c 51%, IId 31%, IIe
39%. (b) Compounds Ib, c were prepared by chlorin-
ation in DMF at 40 C and the molar ratio initial
compound chlorine 1: 4. At these conditions yield of
compound IIb was 72%, yield of compound IIc 34%.
(c) The chlorination in a mixture DMF acetic acid,
1: 5, at 30 C and molar ratio initial compound
chlorine from 1: 2 to 1: 4 afforded IIa in 68% yield,
at 35 45 C and molar ratio initial compound chlorine
from 1: 2 to 1: 3 furnished IIb in 46% yield. (d)
Compounds IIb e were also obtained by chlorination
in CHCl3 at 25 C and complete saturation of the
solution with chlorine. The yields of the reaction
products were as follows: IIb 47%, IIb 71%, IId
39%, IIe 46%.
EXPERIMENTAL
IR spectra of compounds synthesized were
recorded on spectrophotometer UR 20 from KBr
pellets. 1H and 13C NMR spectra were registered
on spectrometer Varian VXR-300 at operating
1
frequencies 300 MHz (for H) and 75.4 MHz (for
13C), TMS was used as external reference.
The reaction mixtures were analyzed by TLC on
Silufol UV-254 plates; solvent chloroform, eluent
benzene hexane, 10: 1, development in UV light.
Compounds Ia, b, VIa, b, VIIIa c were prepared
along procedure described in [11] by acylation of
p-aminophenol(naphthol) and p-phenylenediamine
with an appropriate acyl chloride in a mixture
DMF AcOH, 1: 3. Melting points of compounds
In all runs to the end of the chlorination separated
a precipitate that was recrystallized from acetic acid.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

828
AVDEENKO, MARCHENKO
N,N -Diacetyl-2,5-dichloro-1,4-phenylenedi-
N-Acetyl(aroyl)-2,3,5,6-tetrachloro-1,4-benzo-
amine (IXa). Through a solution of 0.5 g of com-
pound VIIIa in 3 ml of DMF or of mixture DMF
acetic acid, 1: 5, was passed chlorine gas at a rate
quinone imines (IVa e). (a) Through a solution of
0.5 g of compound Ib e in 3 ml of DMF was
passed chlorine gas at a rate 15 20 ml/min till the
additional weight of the mixture corresponded to the
desired molar ratio initial compound chlorine, 1: 5.
The temperature was maintained in the 10 70 C
range. The reaction products IVb e were precipitated
from the reaction mixture with water. The oily sub-
stance precipitated solidified within 24 h. The yellow
solid was recrystallized from acetic acid. The highest
yield was obtained with compound IV at 40 C (85%).
The yields of the other compounds were as follows:
IVc 58% (70 C), IVd 38% (70 C), IVe 43% (50 C).
The chlorination at higher temperature and at greater
excess of chlorine is accompanied by hydrolysis of
the reaction product to yield chloranil (V).
1
15 20 ml min till the additional weight of the mix-
ture corresponded to the desired molar ratio initial
compound chlorine, 1: 2 or 1: 3. The temperature
was maintained in the 40 55 C range. To the end of
chlorination separated colorless precipitate of the
reaction product IXa. The product was recrystallized
from DMF. The best yield of compound IXa, 64%,
was obtained at chlorination in the DMF acetic acid
mixture, 1: 5, at 45 C and molar ratio initial
compound chlorine 1: 3.
N,N -Diaroyl-2,5(2,6-,2,3-)dichloro-1,4-phenyl-
enediamines (IXb e, Xb e, XIb e). The chlorina-
tion of compounds VIIIb e was carried out as
described above in DMF or in the mixture DMF
acetic acid, 1: 5, at 25 50 C and molar ratios initial
product chlorine in the range from 1: 2 to 1: 6. The
colorless reaction products consisting of isomer mix-
tures IX, X, XI precipitated to the end of chlorination
and were recrystallized from DMF. The best yield of
the isomer mixtures was obtained at chlorination in
the DMF acetic acid mixture, 1: 5, at 40 C and molar
ratio initial compound chlorine 1: 5. The yields of the
chlorination products were as follows: IXb, Xb, XIb
51%, IXc, Xc, XIc 52%, IXd, Xd, XId 61%, IXe,
Xe, XIe 58%.
(b) The chlorination of compounds IIa c, e was
carried out along the procedure described above in
DMF solution at 50 C and at the ratio initial
compound chlorine 1: 2. The reaction product was
precipitated with water. The precipitates of com-
pounds IVa c, e were recrystallized from acetic acid.
The yields of compounds obtained are as follows:
IVa 63%, IVb 75%, IVc 56%, IVe 79%. (c) Com-
pound IVa was obtained by treating with chlorine
of compound IIIa in DMF at 30 C and molar ratio
compound IIa chlorine 1: 6. The reaction product
was precipitated from the reaction mixture with
water, recrystallized from acetic acid, yield 67%.
Compound IVa was identic to a substance with a
known structure [1].
N,N -Diaroyl-2,5(2,6-,2,3-)dichloro-1,4-benzo-
quinone diimines (XIIb e, XIIIb e, XIVb e) were
prepared by oxidation of isomer mixtures IXb e,
Xb e, XIb e with lead tetraacetate in benzene along
procedure described in [2]. The reaction products
were recrystallized from heptane. The content of
isomers in the mixtures was determined from the cor-
N-Aroyl(acetyl)-2,6-dichloro-1-naphthoquinone
imines VIIa e. Through a solution of 0.5 g of
compound VIb e in 3 ml of DMF was passed
1
chlorine gas at a rate 15 20 ml min till the addi-
1
responding signals on the integration curves in the H
tional weight of the mixture corresponded to the
desired molar ratio initial compound chlorine (from
1: 2 to 1: 8). The temperature was maintained in the
25 65 C range. The yellow reaction products VIIa e
precipitated from the reaction mixture to the end of
chlorination. The products were recrystallized from
acetic acid. The highest yield of chlorination pro-
ducts was observed for compound VIIa at 65 C and
molar ratio initial compound chlorine 1: 5 (41%), for
compound VIIb at 45 C and 1:8 ratio (95%), for
compound VIIc at 40 C and 1:5 ratio (47%), for com-
pound VIId at 60 C and 1: 4 ratio (39%), for
compound VIIe at 65 C and 1: 5 ratio (46%).
NMR spectra. According to elemental analyses in the
isomer mixtures are no substances of the other com-
position.
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CHLORINATION OF N-ACYL DERIVATIVES OF p-AMINOPHENOLS
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