Diazo reactions with unsaturated compounds: XIII. Reactions of p-(buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide with arenediazonium chlorides, 1-aryl-3,3-dimethyltriaz-1-enes, and arenediazonium tetrachlorocuprates(II)

Article abstract of DOI:10.1134/S1070363211030212

p-(Buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide reacted with arenediazonium chlorides, 1-aryl-3,3-dimethyltriaz-1-enes, and arenediazonium tetrachlorocuprates(II) in aqueous acetone in the presence of copper(II) chloride to give the corresponding p-(4-ar

Full text of DOI:10.1134/S1070363211030212

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 566–568. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.V. Smalius, V. M. Naidan, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 3, pp. 471–473.
Diazo Reactions with Unsaturated Compounds:
XIІI.1 Reactions of p-(Buta-1,3-dien-1-ylsulfonyl)benzenesulfon-
amide with Arenediazonium Chlorides, 1-Aryl-3,3-dimethyl-
triaz-1-enes, and Arenediazonium Tetrachlorocuprates(ІІ)
V. V. Smalius and V. M. Naidan
Khmel’nitskii Cherkassy National University, bul. Shevchenko 81, Cherkassy, 18031 Ukraine
e-mail: smalyus@gmail.com
Received February 9, 2010
Abstract—p-(Buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide reacted with arenediazonium chlorides, 1-aryl-
3,3-dimethyltriaz-1-enes, and arenediazonium tetrachlorocuprates(ІІ) in aqueous acetone in the presence of
copper(II) chloride to give the corresponding p-(4-aryl-3-chlorobut-1-en-1-ylsulfonyl)benzenesulfonamides.
DOI: 10.1134/S1070363211030212
We previously showed [1–4] that 1-(p-nitro-
phenylsulfonyl)-, 1-(m-nitrophenylsulfonyl)-, 1-(p-
chlorophenylsulfonyl)-, 1-(p-bromophenylsulfonyl)-,
1-(p-methylphenylsulfonyl)-, 1-(p-methoxyphenylsul-
fonyl)-, and 1-(p-carboxyphenylsulfonyl)buta-1,3-
dienes react with arenediazonium chlorides and 1-aryl-
3,3-dimethyltriaz-1-enes to give the corresponding
chloroarylation products.
azonium chlorides, 1-aryl-3,3-dimethyltriaz-1-enes,
and arenediazonium tetrachlorocuprates(ІІ) in a similar
way to produce p-(4-aryl-3-chlorobut-1-en-1-ylsul-
fonyl)benzenesulfonamides Ia–Ie (Scheme 1, Table 1)
as a result of addition of chlorine and aryl group at the
double bond most distant from the sulfonyl group. The
reactions of p-(buta-1,3-dien-1-ylsulfonyl)benzenesul-
fonamide with arenediazonium tetrachlorocuprates(ІІ)
were carried out in aqueous acetone at 32–34°C, and
the reactions with arenediazonium chloride and 1-aryl-
3,3-dimethyltriaz-1-enes occurred under analogous
In the present study we found that p-(buta-1,3-dien-
1-ylsulfonyl)benzenesulfonamide reacted with arenedi-
Scheme 1.
O
S
H2NSO2
R
O
Ia_Ie
Cl
_N2 RC6H4N2Cl
O
S
RC6H4N=N_N(CH3)2, 2HCl
(RC6H4N2)2CuCl4
_N2
H2NSO2
_
_
.
N2, (CH3)2NH HCl
O
R = H (a), CH3 (b), Br (c), Cl (d), O2N (e).
1
For communication XII, see [1].
566

DIAZO REACTIONS WITH UNSATURATED COMPOUNDS: XIІI.
567
Table 1. Yields, melting points, and elemental analyses of chloroarylation products of p-(buta-1,3-dien-1-ylsulfonyl)-
benzenesulfonamide
Found, %
Calculated, %
Comp.
no.
Yield, %
mp, °C
Formula
N
Hlg
9.32
N
Hlg
9.19
Ia
Ib
Ic
Id
Ie
47 (a), 64 (b), 70 (c)
43 (a), 51 (b), 54 (c)
36 (a), 37 (b), 40 (c)
35 (a), 39 (b), 39 (c)
24 (a), 29 (b), –
185–186
149–150
3.72
3.60
3.06
3.45
6.45
С16Н16СlNO4S2
С17Н18СlNO4S2
С16Н15BrСlNO4S2
С16Н15Сl2NO4S2
С16Н15СlN2O6S2
3.63
3.50
3.01
3.33
6.50
8.90
8.87
189.5–190.5
158–159
24.91
16.77
8.29
24.82
16.87
8.23
195–196
Table 2. 1H NMR spectra of p-(4-aryl-3-chlorobut-1-en-1-ylsulfonyl)benzenesulfonamides Іa–Ie
Comp.
no.
Chemical shifts δ, ppm (J, Hz)
3.13–3.26 m (2H, CH2), 5.05 d.d (1H, CH), 6.95–7.05 m (2H, CH), 7.17–7.24 m (5H, C6H5), 7.67 s (2H, NH2), 7.95 d (2H,
C6H4, J = 8.5), 8.03d (2H, C6H4, J = 8.5)
Ia
Ib
Ic
Id
Ie
2.22 s (2H, CH3), 3.08–3.20 m (2H, CH2), 5.00 d.d (1H, CH), 6.94 d (1H, CH, J = 15), 7.00 t (3H, CH, C6H5, J = 8.5, 8.5), 7.06
d (2H, C6H4, J = 8.0), 7.65 s (2H, NH2), 7.95 d (2H, p-H2NSO2C6H4, J = 8.5), 8.03 d (2H, p-H2NSO2C6H4, J = 8.0)
3.09–3.27 m (2H, CH2), 5.05 d.d (1H, CH), 6.99–7.07 m (2H, CH), 7.18 d (2H, p-BrC6H4, J = 8.0), 7.45 d (2H, p-BrC6H4, J =
8.0), 7.64 s (2H, NH2), 8.00 d (2H, C6H4, J = 9.0), 8.06 d (2H, C6H4, J = 8.0)
3.11–3.29 m (2H, CH2), 5.05 d.d (1H, CH, J = 6.5, 6.0), 6.99–7.07 m (2H, CH), 7.24 d (2H, p-ClC6H4, J = 8.5), 7.31 d (2H, p-
ClC6H4, J = 8.5), 7.65 s (2H, NH2), 7.99 d (2H, C6H4, J = 8.5), 8.06 d (2H, C6H4, J = 8.5)
3.23–3.48 m (2H, CH2), 5.16 d.d (1H, CH), 7.63 s (2H, NH2), 7.09 d (2H, CH), 7.53 d (2H, C6H4, J = 7.5), 8.05 d (4H, C6H4, p-
O2NC6H4), 8.15 d (2H, p-O2NC6H4, J = 8.0)
conditions in the presence of copper(II) chloride. In the
at 6.94 (Ib), multiplet at 6.99–7.07 (Ic, Id), or doublet
at 7.09 ppm (Ie). The CHCl proton signal appeared as
a doublet of doublets at δ 5.05 (Ia–Id) or 5.16 ppm
(Ie). Large spin–spin coupling constants for protons at
the double bond (Іb, J = 15 Hz) indicate trans
orientation of these protons.
latter case (with 1-aryl-3,3-dimethyltriaz-1-enes) hyd-
rochloric acid was also added to the reaction mixture.
Apart from compounds Ia–Ie, the corresponding aryl
chlorides were also formed, while the reactions with 1-
aryl-3,3-dimethyltriaz-1-enes were accompanied by
formation of dimethylamine hydrochloride as well.
Most probably, 1-aryl-3,3-dimethyltriaz-1-enes react
initially with hydrochloric acid to give arenediazonium
chlorides which then react with the diene.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Varian
Gemini-400 spectrometer from solutions in DMSO-d6.
Initial 1-aryl-3,3-dimethyltriaz-1-enes were syn-
thesized by azo coupling of the corresponding
arenediazonium chlorides with dimethylamine [5].
Arenediazonium tetrachlorocuprates(II) were prepared
according to the procedure described in [6].
The yields of Ia–Id in the reactions of p-(buta-1,3-
dien-1-ylsulfonyl)benzenesulfonamide with arenedi-
azonium tetrachlorocuprates(ІІ) were higher than in the
reactions of the same diene with 1-aryl-3,3-di-
methyltriaz-1-enes. The lowest yields of compounds
Ia–Ie were obtained in the reactions of p-(buta-1,3-
dien-1-ylsulfonyl)benzenesulfonamide with arenediazo-
nium chlorides.
4-(4-Chlorobut-2-en-1-ylsulfonyl)benzenesulfon-
amide was synthesized in a way similar to the
synthesis of 4-chloro-1-(p-nitrophenylsulfonyl)but-2-
ene [7] by reaction of 2.3 l of gaseous buta-1,3-diene
with a solution of diazonium salt prepared from 8.6 g
of 4-aminobenzenesulfonamide. Yield 9.2 g (59.5%),
white crystals, mp 200–201°C (from ethanol–water,
The assumed structure of compounds Ia–Ie was
1
well consistent with their H NMR spectra (Table 2)
which clearly displayed signals from protons at the
double bond as a multiplet at δ 6.95–7.05 (Ia), doublet
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

568
SMALIUS, NAIDAN
1
1:2). H NMR spectrum, δ, ppm: 4.16 d (2H, CH2),
4.24 d (2H, CH2), 5.74–5.79 m (2H, CH), 7.65 s (2H,
NH2), 8.04 s (4H, C6H4). Found, %: N 4.69, 4.76.
C10H12ClNO4S2. Calculated: N 4.52%.
water. The precipitate was filtered off and purified by
recrystallization from aqueous ethanol (1:1).
b. The corresponding 1-aryl-3,3-dimethyltriz-1-ene,
0.04 mol, was added to the reaction mixture prepared
as described in a, and 20 ml of 15% hydrochloric acid
(in the synthesis of Ia and Ib), 12 ml of concentrated
hydrochloric acid (Іc, Id), or a mixture of 51 ml of
concentrated hydrochloric acid and 11 ml of
concentrated sulfuric acid (Іe) was added, maintaining
the temperature at 28–30°C. When the reaction was
complete, the product was isolated as described above
in a.
4-(Buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide.
A solution of 6.9 ml of triethylamine in 20 ml of
benzene was added in small portions to a solution of
15.5 g 4-(4-chlorobut-2-en-1-ylsulfonyl)benzenesulfon-
amide in 130 ml of benzene, and the mixture was
heated for 3 h at 70–80°C on a water bath. The pre-
cipitate of triethylamine hydrochloride was filtered off,
the filtrate was evaporated under reduced pressure, and
the precipitate was separated and recrystallized from
ethanol–water (1:2). Yield 6.5 g (47.6%), white
c. A mixture of 80 ml of acetone, 20 ml of water,
9.6 g of 4-(buta-1,3-dien-1-ylsulfonyl)benzenesulfon-
amide, and 0.02 mol of the corresponding arene-
diazonium tetrachlorocuprate(II) was vigorously stir-
red at 32–34°C until gaseous products no longer
evolved. The mixture was then treated as described above.
1
crystals, mp 184–185°C. H NMR spectrum, δ, ppm:
4.92 s (2H, NH2), 5.68d (1H, CH, J = 9.0 Hz), 5.80 d
(1H, CH, J = 17.0 Hz), 6.37–6.44 m (2H, CH2),
7.32d.d (1H, CH, J = 11.0, 11.5 Hz), 8.05 d (2H, C6H4,
J = 8.0 Hz), 8.10 d (2H, C6H4, J = 7.5 Hz). Found, %:
N 4.93, 5.02. С10H11O4S. Calculated: N 5.12%.
REFERENCES
4-(Aryl-3-chlorobut-1-en-1-ylsulfonyl)benzenesul-
fon-amides Ia–Ie (general procedures). a. A three-
necked flask was charged with 60 ml of acetone, 10 ml
of water, 1.6 g of copper(II) chloride, and 10.92 g of 4-
(buta-1,3-dien-1-ylsulfonyl)benzenesulfonamide, the
mixture was heated to 30–32°C, and a solution of
arenediazonium chloride prepared from 0.04 mol of
the corresponding aromatic amine, 13.6 ml of con-
centrated hydrochloric acid, and 2.9 g of sodium nitrite
was added dropwise under continuous stirring. Solu-
tions of benzene-, 4-methylbenzene-, 4-chloro-
benzene-, and 4-bromobenzenediazonium chlorides
were preliminarily neutralized to pH 3–4 by adding
NaHCO3. When the addition of arenediazonium salt
was complete, the mixture was stirred until gaseous
products no longer evolved and poured into 300 ml of
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