Chlorosulphonation of 2-anilino-1,4-naphthoquinone and synthesis of newer sulphonyl derivatives

Article abstract of DOI:10.1080/10426500490466869

Synthesis of 2-anilino-1,4-napthoquinone-3-sulphonyl chloride (2) was achieved from the reaction of the title compound with chlorosulphonic acid. The interesting derivative 2 was used as a building block for synthesis of the sulphonyl derivatives 3-24. All these sulphonyl derivatives were characterized by the physical and spectral data (IR, Mass, ¹H- and ¹³C NMR spectra).

Full text of DOI:10.1080/10426500490466869

Phosphorus, Sulfur, and Silicon, 179:1907–1922, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490466869
CHLOROSULPHONATION OF
2-ANILINO-1,4-NAPHTHOQUINONE AND SYNTHESIS
OF NEWER SULPHONYL DERIVATIVES
Moged A. Berghota and Nayef S. Almuaikelb
Chemistry Department, Faculty of Science, Mansoura
University, Mansoura, Egypt;a and Aljouf, Teachers College,
Skaka Aljouf, Saudia Arabiab
(Received November 26, 2003; accepted January 25, 2004)
Synthesis of 2-anilino-1,4-napthoquinone-3-sulphonyl chloride (2) was
achieved from the reaction of the title compound with chlorosulphonic
acid. The interesting derivative 2 was used as a building block for syn-
thesis of the sulphonyl derivatives 3–24. All these sulphonyl derivatives
were characterized by the physical and spectral data (IR, Mass, 1H- and
13C NMR spectra).
Keywords: 2-Anilino-1,4-naphthoquinone; chlorosulphonation; sulpho-
nylpyrazole; sulphonylpyrazolone; sulphonylthiazolidinaone; sulpho-
nyltriazole
INTRODUCTION
2,3-Disubstituted-1,4-naphthoquinones posseses biological importa-
nce.1–5 On the other hand, the biological activity of certain pyrazoles,6,7
thiazolidinones,8,9 and sulphonyl derivatives10,11 have been stud-
ied. In view of these results and in continuation of our studies
on 1,4-naphthoquinones,12–16 we considered it more attractive to
chlorosulphonate a naphthoquinonoide compound so that it has a
reactive position toward electrophiles. The chlorosulphonation of such
compounds is not yet quoted in the chemical literature. 2-Anilino-
1,4-nahthoquinone (1) used as a starting material for this reaction
and synthesis of naphthoquinonoid systems contain sulphonamides,
sulphonyl pyrazoles, sulphonyl thiazolidinones, and sulphonyl triazoles
of expected biologiacal activity.
Address correspondence to Moged A. Berghot, Chemistry Department, Faculty of Sci-
ence, Mansoura University, Mansoura, Egypt. E-mail: dal mag@hotmail.com
1907

1908
M. A. Berghot and N. S. Almuaikel
RESULTS AND DISCUSSION
Chlorosulphonation of 1 was accomplished by using excess of chlorosul-
phonic acid to give 2-anilino-1,4-naphthoquinone-3-sulphonyl chloride
2. Then, compound 2 on refluxing with ammonium hydroxide yielded
primary sulphonamide derivative 3a. The secondary sulphonamide
derivatives 3b–d were achieved when 2 was reacted with aniline,
P-toulidine, and P-anisidine, respectively. When 2 was treated with
piperidine, morpholine, N-methyl piperazine, and N-phenyl piperazine,
teriary sulphonamide derivatives 4a–d were produced, respectively
(Scheme 1).
When 3a was reacted with an appropriate aromatic aldehyeds
namely benzaldehyde, O-anisaldehyde, and P-chlorobenzaldehyd un-
der reflux in acetic acid and in the prescence of anhydrous sodium ac-
etate, Shiff’s base of types 4a–c were obtained. Reaction of 4a with thio-
glycolic acid in dry benzine thiazolidinone derivative 5 was produced.
Mannich’s reaction of 5 with formaldehyde and in the prescence of mor-
pholine gave 5-morpholinomethyl derivative 6. Moreover, 5 was con-
densed with benzaldehyde to give benzylidene derivative 7 (Scheme 2).
On the other hand, sulphonylhydrazine derivative 9 was produced in
about 80% yield from the reaction of 2 with hydrazine hydrate in pres-
cence of pyridine. In ethanolic solution, the corresponding hydrazone
10 was obtained from the reaction of 9 with ethyl acetoacetate. Reflux-
ing 10 in acetic acid yielded the cyclized product 11, while the cyclized
product 12a was formed directly from reaction of 9 with acetylacetone
in acetic acid. In a similar manner, 9 was reacted with chalcone, which
was synthesized from benzaldehyde and acetophenone17 when 12b was
obtained (Scheme 3).
Similarly, reaction of 9 with 2-(hydroxymethylene) cyclohexanone18
afforded tetrahydro indazole derivative 13 as an alone product (TLC).
Hydrazone 14 was furnished from condensation of 9 with acetophenone
in ethanol with traces of acetic acid. On reaction with phosphrous oxy-
chloride and dimethylformamide, this hydrazone lead to the formation
of 4-formyl-3-phenyl-1-pyrazolyl derivative 15 (Scheme 3).
Moreover, refluxing of 9 with α-cyanoacetophenone19 in the presence
of ethanole-acetic acid gave 5-amino-pyrazolyl derivative 16, while 3-
amino-pyrazolyl derivative 17 was yielded under the same conditions
from reaction of 9 with benzoylacetamide.20 Analogously, 9 was re-
acted with benzoylacetic acid hydrazide21 to get 3-hydrazino-pyrazlolyl
derivative 18, which was acetylated to achieve triazolo-pyrazole deriva-
tive 19. The latter derivative 19 was also synthesized from reaction of
9 with N-acetyl benzoylacetic acid hydrazide in acetic acid-sodium ac-
etate (Scheme 4).

Synthesis of New Sulphonyl Derivatives
1909
SCHEME 1

1910
M. A. Berghot and N. S. Almuaikel
SCHEME 2
Furthermore, treatment of 9 with phenylisothiocyanate afforded
the corresponding thiocarbamoyl hydrazino derivative 20, which was
cyclized with phenacyl bromide to produce thiazoline derivative 21.
Compound 20 was also reacted with ethyl chloroacetate to give thiazo-
lidinone derivative 22. Condensation of 22 with o-anisaldehyde in the
presense of triethylamine afforded 23 (Scheme 5).
Finally, triazole derivative 24 was yeilded from the reaction of 9 with
benzoyl cyanide22 in molat ratio 2:1. The formation of 24 involves a
somewhat similar pathway to that reported for the formation of sugar
osatriazoles from osazone.20 The probable reaction mechanism is shown
in Scheme 6. The reaction between benzoyl cyanide and 9 apparently
involves formation of the intermediate A, which immediately cyclized
to 24 by loses a molecule of sulphonamide derivative 3a.
1
The physical, IR, H and 13C NMR data of the newly synthesized
compounds are given in Tables I, II, III, and IV respectively.

Synthesis of New Sulphonyl Derivatives
1911
SCHEME 3

1912
M. A. Berghot and N. S. Almuaikel
SCHEME 4
EXPERIMENTAL
All melting points are uncorrected and were determined in capil-
lary tube and Gallenkamp melting points apparatus. IR spectra were
recorded in KBr on a Backman Infrared spectrophotometer PU, 9712
1
using KBr discs. H and 13C NMR spectra were obtained on a Bruker
AC 200(H:300, C:75 MHz) spectrometer with TMS as internal stan-
dard. The solvent were DMSO-d6 and CDCl3. δ-values are given in
ppm. Mass spectra were recorded on SSQ, 7000 mass spectrometer at
70 eV. Microanalysis were performed at the microanalytical unit at
Cairo University.

Synthesis of New Sulphonyl Derivatives
1913
SCHEME 5
2-Anilino-1,4-napthoquinone-3-sulphonyl Chloride (2)
To a solution of 1 (2.4 g, 0.01 mol) in chloroform (100 ml), excess of chloro-
sulphonic acid (11.6 ml, 0.1 mol) was added with stiring for 2 h The mix-
ture was kept at 80–100◦C for 20 h and then cooled. The solid product
was filtered off and crystallized from dimethyformamide to give 2.
2-Anilino-1,4-napthoquinone-3-sulphonamide (3)
A mixture of 2 (3.5 g, 0.01 mol), ammonium hydroxide (5 ml), or the
proper amino compound (0.01 mol), namely aniline, p-toluidine,
p-anisidine, piperidine, morpholine, N-methylpiperazine, and

1914
M. A. Berghot and N. S. Almuaikel
SCHEME 6
N-phenylpiperazine in absolute ethanol (100 ml) and in the pres-
ence of pyridine (1 ml) was heated under reflux for 8 h. Then it was
cooled, filtered off, and crystallized from acetic acid to give 3a–d and
4a–d, respectively.
2-Anilino-1,4-napthoquinone-3-benzylidine
Sulphonamide (5)
A mixture of sulphonamide 3a (3.2 g, 0.01 mol) and benzaldehyde
(1 ml, 0.01 mol) was refluxed in ethanol (50 ml) for 5 h. The solid was

Synthesis of New Sulphonyl Derivatives
1915
TABLE I Physical and Analytical Data of the Newly Synthesized
Compounds 2–24
Comp.
no.
m.p.
(◦C)
Mol. formula
(mol. wt.)
Yield MS.
Calcd/Found analysis(%)
(%)
M+
C
H
N
S
2
3a
3b
3c
3d
4a
4b
4c
4d
5
220–221 C16H10NO4S Cl
(347.8)
70
347 55.25/ 2.89/
54.91 3.13
328 58.52/ 3.69/
58.38 3.88
404 65.34/ 3.99/
65.06 4.13
66.01/ 4.34/
65.90 4.45
63.57/ 4.18/
63.75 4.32
396 63.61/ 5.09/
63.51 4.89
398 60.29/ 4.55/
60.46 4.73
4.03/
3.82
8.53/
8.28
6.92/
7.09
6.70/
6.89
6.45/
6.61
7.07/
6.69
7.03/
6.91
9.22/
8.93
9.77/
9.62
7.93/
7.71
7.66/
7.43
7.38/
7.21
8.09/
7.81
8.05/
8.31
7.79/
7.51
6.77/
6.89
7.70/
7.49
280
263–264
271–272
258
C16H12N2O4S
(328.4)
C22H16N2O4S
(404.4)
C23H18H2O4S
(418.5)
62
75
71
67
65
65
61
70
64
68
70
75
80
68
65
72
85
66
57
68
77
—
—
C
23H18N2O5S
(434.5)
293–295
298
C
21H20N2O4S
(396.5)
C20H18N2O5S
(398.4)
>300
C
C
C
21H21N3O4S
(411.5)
26H23N3O4S
(473.5)
23H16N2O4S
(416.5)
—
61.29/ 5.16/ 10.21/
61.01
473 65.95/ 4.90/
66.21 5.12
416 66.33/ 3.87/
66.61 3.99
490 61.21/ 3.70/
60.91 3.93
65.71/ 3.91/
65.88 4.11
489 61.10/ 4.62/
60.87 4.51
342 56.12/ 3.23/ 12.27/
5.34
10.40
8.87/
9.03
6.73/
6.96
5.71/ 13.07/
5.38 12.81
4.94/ 11.32/
4.69 11.58
7.13/ 10.87/
>300
233–234
281
6
C25H18N2O5S2
(490.5)
7
>300
C31H22N2O5S2
(566.6)
—
8
255
C30H27N3O6S2
(589.7)
6.92
10.61
9.37/
9.61
7.04/
6.83
7.84/
8.03
7.87/
8.03
6.03/
5.83
7.99/
8.18
7.20/
6.92
6.63/
6.84
6.82/
6.58
9
243–244
210–212
280–281
273–275
277–278
230
C
16H12N3O4S
(342.4)
22H21N3O6S
(455.5)
55.88
455 58.01/ 4.65/
57.80 4.91
3.71
12.00
9.23/
8.98
10
11
12a
12b
13
14
15
16
C
C20H15N3O5S
(409.4)
409 58.67/ 3.69/ 10.26/
58.43 3.91 10.01
407 61.90/ 4.21/ 10.31/
C
C
C
C
C
21H17N3O4S
(407.4)
31H21N3O4S
(531.6)
23H19N3O2S
(401.5)
24H19N3O4S
(445.5)
61.68
531 70.04/ 3.98/
69.81 4.18
3.96
10.58
7.90/
8.11
—
68.80/ 4.77/ 10.47/
69.03
445 64.70/ 4.30/
64.43 4.57
483 64.58/ 3.55/
64.79 3.77
4.51
10.69
9.43/
9.71
8.69/
8.41
259–260
293–294
>300
26H17N3O5S
(483.5)
C25H18N4O4S
(470.5)
—
63.82/ 3.85/ 11.91/
64.03 4.11 12.09
(Continued on next page)

1916
M. A. Berghot and N. S. Almuaikel
TABLE I Physical and Analytical Data of the Newly Synthesized
Compounds 2–24 (Continued)
Comp.
no.
m.p.
(◦C)
Mol. formula
(mol. wt.)
Yield MS.
Calcd/Found analysis (%)
(%)
M+
C
H
N
S
17
18
19
20
21
22
23
24
>300
290–292
263
C25H18N4O4S
(470.5)
C25H19N5O4S
(485.5)
C27H19N5O4S
(509.5)
C23H18N4O4S2
(478.5)
61
470 63.82/ 3.85/ 11.91/
63.99 3.61 11.73
485 61.84/ 3.94/ 14.43/
62.01 4.19 14.62
509 63.64/ 3.76/ 13.75/
63.83 3.92 13.92
6.82/
7.10
6.61/
6.82
6.29/
6.51
78
68
76
68
57
81
72
>300
243
478 57.73/ 3.79/ 11.71/ 13.40/
57.52 3.93 11.51 13.21
578 64.35/ 3.83/ 9.68/ 11.08/
64.16 3.99 9.42 10.91
518 57.90/ 3.50/ 10.80/ 12.37/
58.13 3.83 11.03 12.21
62.25/ 3.80/ 8.80/ 10.07/
62.39 3.99
471 61.13/ 3.64/ 14.85/
60.91 3.82 15.09
C31H22N4O4S2
(578.6)
266
C25H18N4O5S2
(518.5)
275
C33H24N4O6S2
(636.7)
—
8.62
9.89
6.81/
7.03
>300
C
24H17N5O4S
(471.5)
separated on cooling, filtered off, and recrystallized from ethanol to
give 5.
2-Anilino-1,4-napthoquinone-3-sulphonyl Hydrazine (9)
A mixture of 2 (3.4 g, 0.01 mol) and hydrazine hydrate (0.5 ml, 0.01 mol)
in ethanol (50 ml) was refluxed for 10 h. The formed solid after cooling
was filtered off and crystallized from methanol to give 9.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-(ethyl-2ꢀ-
oxo-butyrate) Hydrazone (10)
A mixture of 9 (0.3 g, 0.01 mol) and ethyl acetoacetate (2 ml, 0.01 mol)
in ethanol (50 ml) was heated at 80◦C for 3 h. The mixture was cooled,
and the formed solid was filtered off and crystallized from ethanol to
give 10.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ-methyl-5ꢀ-
pyrazolone (11)
A mixture of hydrazone 10 (4.5 g, 0.01 mol) and acetic acid (50 ml) was
heated under reflux for 3 h. The mixture was left to cool. The formed
solid was filtered off and crystallized from acetic acid to give 11.

Synthesis of New Sulphonyl Derivatives
1917
TABLE II IR Spectral Data of the Compounds 2–24
Comp.
no.
ν, cm−1
2
3210 (NH), 1686 (C O), 1626 (C C), 1335 ( NSO2 ), 1205 ( SO2 )
3a
3b
3c
3d
4a
3426, 3110 (NH2, NH), 1688 (C O), 1614 (C C), 1325 ( NSO2 ), 1220 ( SO2 )
3329, 3180 (NH), 1683 (C O), 1623 (C C), 1320 ( NSO2 ), 1214 ( SO2
3224, 3110 (NH), 1683 (C O), 1604 (C C), 1326 ( NSO2 ), 1205 ( SO2
3315, 3200 (NH), 1686 (C O), 1612 (C C), 1305 ( NSO2 ), 1218 ( SO2
)
)
)
3212 (NH), 2910, 2895 (CH2), 1683 (C O), 1620 (C C), 1322 ( NSO2 ), 1208
SO2
(
)
4b
4c
3173 (NH), 2854 (CH2), 1681 (C O), 1623 (C C), 1326 ( NSO2 ), 1223 ( SO2
3208 (NH), 2936, 2812 (CH2), 1683 (C O), 1613 (C C), 1328 ( NSO2 ), 1210
)
(
SO2
3278 (NH), 2913, 2808 (CH2), 1686 (C O), 1623 (C C), 1322 ( NSO2 ), 1208
SO2
3122 (NH), 1683 (C O), 1643 (C N), 1611 (C C), 1328 ( NSO2 ), 1226 ( SO2
3208 (NH), 1682, 1665 (C O), 1603 (C C), 1329 ( NSO2 ), 1180 ( SO2
)
4d
(
)
5
6
7
8
)
)
3180 (NH), 1683, 1677 (C O), 1628, 1618 (C C), 1324 ( NSO2 ), 1220 ( SO2
3210(NH), 2932, 2893 (CH2), 1680, 1676 (C O), 1616 (C C), 1328( NSO2 ),
)
1207 ( SO2
3450, 3253, 3182 (NH2, NH), 1688 (C O), 1622 (C C), 1325( NSO2 ), 1223
SO2
3110, 3050 (NH), 1686 (C O), 1663 (C N), 1621 (C C), 1320 ( NSO2 ), 1225
SO2
)
9
(
)
10
(
)
11
3212 (NH), 1682 (C O), 1650 (C N), 1613 (C C), 1326 ( NSO2 ), 1222 ( SO2
3250 (NH), 1688 (C O), 1643 (C N), 1603 (C C), 1332 ( NSO2 ), 1208 ( SO2
3192 (NH), 1680 (C O), 1635 (C N), 1612 (C C), 1326 ( NSO2 ), 1225 ( SO2
3210 (NH), 2912, 2906 (CH2), 1680 (C O), 1644 (C N), 1610 (C C), 1338
)
)
)
12a
12b
13
(
NSO2 ), 1223 ( SO2
3286, 3205 (NH), 1686 (C O), 1644 (C N), 1610 (C C), 1325 ( NSO2 ), 1225
SO2
3128 (NH), 1685, 1680 (C O), 1632 (C N), 1606 (C C), 1332 ( NSO2 ), 1230
SO2
3310, 3206 (NH2, NH), 1686 (C O), 1641 (C N), 1606 (C C), 1325 ( NSO2 ),
1220( SO2
3322, 3288, 3112 (NH2, NH), 1688 (C O), 1635 (C N), 1611 (C C), 1330
NSO2 ), 1208 ( SO2
3405, 3392, 3238, 3131 (NH2, NH), 1686 (C O), 1648 (C N), 1620 (C C), 1332
NSO2 ), 1220 ( SO2
3225, 3116 (NH), 1682 (C O), 1640, 1632 (C N), 1611 (C C), 1326 ( NSO2 ),
1220 ( SO2
3450, 3320, 3183 (NH), 1680 (C O), 1613 (C C), 1582 (N-C S), 1320 ( NSO2 ),
1224 ( SO2
3225, 3130 (NH), 1683 (C O), 1626 (C C), 1643 (C N), 1338 ( NSO2 ), 1226
SO2
3205, 3110 (NH), 1683 (C O), 1635 (C N), 1613 (C C), 1326 ( NSO2 ), 1226
SO2
3205, 3132 (NH), 1682 (C O), 1636 (C N), 1616 (C C), 1333 ( NSO2 ), 1225
SO2
3330, 3128 (NH2, NH), 1683 (C O), 1642, 1637 (C N), 1611 (C C), 1335
NSO2 ), 1226 ( SO2
)
14
15
16
17
18
19
20
21
22
23
24
(
)
(
)
)
(
)
(
)
)
)
(
)
(
)
(
)
(
)

1918
M. A. Berghot and N. S. Almuaikel
TABLE III 1H-NMR Spectral Data of Some New Synthesized Compounds
Comp.
no.
δ, ppm
3a
3b
3c
9.8 (s, 2H, NH2), 7.3–7.9 (m, 9H, Ar-H), 6.1 (s, 1H, NH, D2O exchangeable)
9.1 (s, 1H, NH), 7.0–7.5 (m, 14H, Ar-H), 6.3 (s, 1H, NH, D2O exchangeable)
2.2 (s, 3H, Ar-CH3), 5.8 (s, 1H, NH), 7.1–7.8 (m, 13H, Ar-H), 9.2 (s, 1H, NH,
D2O exchangeable)
3d
4a
4b
4c
4d
5
3.5 (s, 3H, Ar-OCH3), 5.9 (s, 1H, NH), 6.9–7.8 (m, 13H, Ar-H), 9.7 (s, 1H, NH,
D2O exchangeable)
1.9–2.5 (m, 10H, pipridine-H), 6.2 (s, 1H, NH, D2O exchangeable), 7.1–7.8 (m,
9H, Ar-H)
3.5–3.8 (m, 8H, morpholine-H), 6.0 (s, 1H, NH, D2O exchangeable), 7.0–7.3
(m, 9H, Ar-H)
2.2–2.4 (m, 8H, piprazine-H), 3.4 (s, 3H, N-CH3), 5.8 (s, 1H, NH, D2O
exchangeable), 7.3–7.6 (m, 9H, Ar-H)
3.1–3.3 (m, 8H, piprazine-H), 6.1 (s, 1H, NH, D2O exchangeable), 6.9–7.7 (m,
4H, Ar-H)
5.8 (s, 1H, NH, D2O exchangeable), 6.3 (s, 1H, N CH), 7.1–7.4 (m, 14H,
Ar-H), 8.9 (s, 1H, NH)
10
11
12a
1.3 (t, 3H, CH2CH3), 2.2 (s, 3H, CH3-C N), 3.4 (s, 2H, CH2CO), 4.1 (q, 2H,
CH2CH3), 5.6 (s, 1H, NH), 7.1–7.6 (m, 9H, Ar-H), 11.1 (br, 1H, NH)
2.3 (s, 3H, CH3
Ar-H)
C N), 3.5 (s, 2H, CH2CO), 5.6 (s, 1H, NH), 6.8–7.3 (m, 9H,
2.5 (s, 6H, 2CH3), 4.1 (s, 1H, C4 H pyrazole), 5.8 (s, 1H, NH), 7.1–7.5 (m, 9H,
Ar-H)
12b
13
3.8 (s, 1H, C4 H pyrazole), 5.7 (s, 1H, NH), 6.9–7.8 (br, 19H, Ar-H)
1.7–2.0, 2.4–2.8 (m, 8H, 4CH2), 6.6 (s, 1H, C3-H pyrazole), 5.8 (s, 1H, NH),
7.0–7.4 (m, 9H, Ar-H)
14
15
3.1(s, 3H, CH3 C N), 5.6(s, 1H, NH), 6.8–7.7(m, 14H, Ar-H), 9.7 (br, 1H, NH)
5.6 (s, 1H, NH, D2O exchangeable), 7.2–8.5 (m, 15H, Ar-H, C5 H pyrazole),
10.2 (s, 1H, CHO)
16
17
18
5.8 (s, 1H, NH), 6.5 (s, 1H, C3 H pyrazole), 7.3–7.6 (m, 14H, Ar-H), 8.9 (br,
2H, NH2)
3.9 (s, 1H, C4-H pyrazole), 5.6 (s, 1H, NH), 7.1–7.5 (m, 14H, Ar-H), 9.3 (br, 2H,
NH2)
3.6 (s, 1H, C4-H pyrazole), 5.5 (s, 1H, NH), 5.8 (s, 2H, NH2), 7.0–7.8 (m, 14H,
Ar-H), 9.1 (s, 1H, NH)
19
21
2.8 (s, 3H, CH3 C N), 5.1 (s, 1H, NH), 7.2–7.7 (m, 14H, Ar-H)
3.4 (br, 1H, NH), 5.1 (s, 1H, C5 H thiazoline), 5.8 (s, 1H, NH), 6.7–7.6 (m,
19H, Ar-H)
22
24
3.9 (s, 2H, C5 H thiazolidinone), 4.1 (s, 1H, NH), 5.7 (s, 1H, NH), 7.1–7.3 (m,
14H, Ar-H)
5.8 (s, 1H, NH), 6.2 (br, 2H, NH2), 6.8–7.9 (m, 14H, Ar-H)
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-
3ꢀ, 5ꢀ-dimethyl Pyrazole (12a)
A mixture of 9 (3.4 g, 0.01 mol) and acetylacetone (2 ml, 0.02 mol) in
acetic acid (50 ml) was refluxed for 5 h. The mixture was left to cool.

Synthesis of New Sulphonyl Derivatives
1919
TABLE IV 13C-NMR Spectral Data of the Compounds 3c, 3d, 4a–d, 11, 13,
and 22
Comp.
no.
δ, ppm
3c
182.3, 181.6, 152.0, 151.8, 140.0, 138.1, 133.9, 132.8, 128.1, 126.7, 126.3, 126.2,
125.9, 125.7, 125.3, 125.2, 124.8, 124.6, 124.3, 124.2, 124.0, 123.8, 222.3
181.6, 181.0, 151.7, 151.2, 140.3, 137.8, 133.8, 132.7, 127.9, 126.6, 126.3,
126.1, 126.0, 125.8, 125.6, 125.5, 125.3, 125.2, 124.8, 124.5, 124.1, 35.6
181.8, 181.2, 152.2, 151.8, 140.3, 133.9, 133.4, 131.1, 126.5, 125.8,
125.4, 125.2, 124.8, 124.6, 124.1, 123.7, 37.8, 34.9, 29.6, 26.5, 25.3
182.3, 181.6, 153.1, 151.6, 140.1, 134.2, 133.8, 131.6, 126.8, 125.1,
125.0, 124.8, 124.6, 124.5, 124.0, 123.7, 39.6, 38.2, 37.7, 37.3
181.6, 181.0, 152.8, 152.0, 140.9, 134.8, 133.7, 132.1, 127.1, 126.2,
125.6, 125.3, 124.7, 124.6, 124.3, 123.9, 41.0, 39.8, 35.6, 34.8, 22.8
182.1, 181.8, 152.5, 149.8, 140.4, 136.6, 133.8, 133.1, 126.8, 126.4, 125.8, 125.7,
125.5, 125.1, 124.6, 124.4, 124.6, 123.9, 123.8, 123.5, 123.4, 123.1, 41.3,
40.1, 36.5, 35.8
3d
4a
4b
4c
4d
11
13
22
181.9, 180.8, 170.3, 156.3, 154.2, 123.8, 141.3, 134.9, 134.6, 131.6,
127.3, 125.8, 125.8, 124.8, 124.5, 124.2, 123.9, 122.4, 44.6
182.1, 181.7, 154.0, 153.8, 141.1, 140.2, 134.6, 134.0, 131.5, 126.3,
125.2, 124.9, 124.7, 124.6, 124.4, 124.1, 123.8, 120.9, 24.0, 23.3, 22.6, 20.8
182.3, 181.6, 170.4, 154.3, 154.1, 153.6, 141.0, 134.5, 134.1, 131.8,
127.0, 126.1, 124.9, 124.6, 124.2, 124.0, 123.9, 120.8, 43.0
The formed solid was filtered off and crystallized from acetic acid to
give 12a.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ,5ꢀ-
diphenyl Pyrazole (12b)
A mixture of 9 (3.4 g, 0.01 mol), benzal actophenone (2 g, 0.01 mol) and
a few drops of pipridine in ethanol (50 ml) was refluxed for 9 h. The mix-
ture was left to cool. The formed solid was filtered off and crystallized
from ethanol to give 12b.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-4ꢀ,5ꢀ,6ꢀ,7ꢀ-
tetrahydro-1H-indazole (13)
A mixture of 9 (3.4 g, 0.01 mol) and 2-hydroxymethylene cyclohexanone
(1.2 g, 0.01 mol) in ethanol (50 ml) containing a few drops of hydrochloric
acid was refluxed for 3 h. The mixture was concentrated and was left
to cool. The formed solid was filtered off and crystallized from ethanol
to give 13.

1920
M. A. Berghot and N. S. Almuaikel
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-
(acetophenono)hydrazone (14)
A mixture of 9 (3.4 g, 0.01 mol) and acetophenone (1.2 ml, 0.01 mol)
in ethanol (50 ml) containing a few drops of acetic acid was refluxed
for 6 h. The mixture was concentrated and was left to cool. The formed
solid was filtered off and crystallized from ethanol to give 14.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ-phenyl-4ꢀ-
formyl-pyrazole (15)
To the Vilsmeir Huck Complex, prepared from dimethylformamide
(10 ml) and phosphrous oxychloride (1.5 g, 0.01 mol) at 0◦C, the hydra-
zone 14 (4.4 g, 0.02 mol) was added and the reaction mixture was heated
for 2 h. The reaction mixture was cooled and poured into ice-cold water.
The product which separated on neutralization with sodium bicarbon-
ate was filtered off and crystallized froom ethanol/dimethylformamide
to give 15.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-5ꢀ-amino-4ꢀ-
phenyl-pyrazole (16)
A mixture of 9 (3.4 g, 0.01 mol) and α-cyano-acetophenone (1.4 g,
0.01 mol) was refluxed in ethanol (50 ml) containing acetic acid (50 ml)
for 5 h. The reaction mixture was left to cool. The formed solid was
filtered off, washed with water, and crystallized from ethanol to give
16.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ-amino-5ꢀ-
phenyl-pyrazole (17)
A mixture of 9 (3.4 g, 0.01 mol) and benzoylacetamide (1.6 g, 0.01 mol)
was refluxed in ethanol (50 ml) containing acetic acid (50 ml) for 3 h.
The reaction mixture was left to cool. The formed solid was filtered off,
washed with water, and crystallized from acetic acid to give 17.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ-
hydrazino-5ꢀ-phenyl-pyrazole (18)
A mixture of 9 (3.4 g, 0.01 mol) and benzoylacetic acid hydrazide
(1.7 g, 0.01 mol) was refluxed in ethanol (50 ml) containing acetic acid
(50 ml) for 3 h. The reaction mixture was left to cool. The formed solid
was filtered off, washed with water, and crystallized from ethanol to
give 18.

Synthesis of New Sulphonyl Derivatives
1921
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-3ꢀ-methyl-5ꢀ-
phenyl-1ꢀ,2ꢀ,4ꢀ-triazolo[4,5-b]pyrazole (19)
a) A mixture of 18 (4.8 g, 0.01 mol) in acetic anhydride (50 ml) was
heated for 3 h and then left to cool. The formed solid was filtered off
and crystallized from ethanol to give 19.
b) A mixture of 9 (3.4 g, 0.01 mol) and N-acetyl benzoylacetic acid
hydrazide (2.2 g, 0.01 mol) in ethanol (100 ml) containing aceti acid
(5 ml) was refluxed for 5 h and then left to cool. The formed solid was
filtered off and crystallized from ethanol to give 19.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-
thiocarbamoyl Hydrazine (20)
A solution of 9 (3.4 g, 0.01 mol) in ethanol (100 ml) was stirred with
phenyl isothiocyanate (1.3 ml, 0.01 mol) for 1 h at room temperature
and then water (5 ml) was added. The formed solid was filtered off and
crystallized from methanol to give 20.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-(3ꢀ,4ꢀ-
diphenyl thiazolin-2ꢀ-ylidene) Hydrazine (21)
To a solution of 20 (4.7 g, 0.01 mol) in chloroform (50 ml) phenacyl
bromide (2 g, 0.01 mol) was added. The mixture was stirred for 1 h. The
solvent was removed under reduced pressure. The residue was dissolved
in ethanol and then treated with a solution of saturated sodium acetate
(20 ml). The formed solid was filtered and crystallized from methanol
to give 21.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-(3ꢀ-phenyl-
4ꢀ-thiazolidinon-2ꢀ-ylidene) Hydrazine (22)
A mixture of 20 (4.7 g, 0.01 mol) in absolute ethanol (50 ml), ethyl
chloroacetate (1.2 g, 0.01 mol) and anhydrous sodium acetate (1.7 g,
0.02 mol) was refluxed for 2 h. Water (20 ml) was added. The formed
solid was filtered off and crystallized from methanol to give 22.
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-[(3ꢀ-phenyl-
5ꢀ-benzylidene-4ꢀ-thiazolidinon-2ꢀ-ylidene)] Hydrazine
(23)
A mixture of 22 (5.1 g, 0.01 mol) in methanol, O-anisaldehyde (1.3 g,
0.01 mol) and triethylamine (1 ml) was heated under reflux for 10 h.
The formed solid was filtered and recrystallized from ethanol to give
23.

1922
M. A. Berghot and N. S. Almuaikel
2-Anilino-1,4-napthoquinone-3-sulphonyl-N-5ꢀ-phenyl-4ꢀ-
amino-2H-1ꢀ,2ꢀ,3ꢀ-triazole (24)
To benzoyl cyanide (1.3 g, 0.01 mol) was added 9 (3.4 g, 0.01 mol) during
10 min. The reaction mixture was stirred for 2 h. The mixture was re-
fluxed at 80◦C for 3 h, left to cool, and washed with diluted hydrochloric
acid (2 × 5 ml). The formed solid was filtered off and recrystallized from
ethanol to give 24.
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