Diazo reactions with unsaturated compounds: IX. ortho-, meta-, and para-nitrophenylsulfonyl-1,3-butadienes in reaction with 1-aryl-3,3-dimethyl-1- triazenes

Article abstract of DOI:10.1007/s11176-005-0275-1

1-(m-Nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-1,3-butadienes in aqueous acetone in the presence of HCl and copper(I) or copper(II) chloride react with 1-aryl-3,3-dimethyl-1-triaenes to form 1-(m-nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfony

Full text of DOI:10.1007/s11176-005-0275-1

Russian Journal of General Chemistry, Vol. 75, No. 4, 2005, pp. 580 582. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005,
pp. 619 621.
Original Russian Text Copyright
2005 by Naidan, Smalius.
Diazo Reactions with Unsaturated Compounds:
IX. ortho-, meta-, and para-Nitrophenylsulfonyl-1,3-butadienes
1
in Reaction with 1-Aryl-3,3-dimethyl-1-triazenes
V. M. Naidan and V. V. Smalius
Khmel’nitskii National University, Cherkassy, Ukraine
Received October 15, 2003
Abstract 1-(m-Nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-1,3-butadienes in aqueous acetone in
the presence of HCl and copper(I) or copper(II) chloride react with 1-aryl-3,3-dimethyl-1-triaenes to form
1
-(m-nitrophenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-butenes, respectively. 1-(o-Nitro-
phenylsulfonyl)-1,3-butadiene fails to react in similar conditions.
We previously showed [1 4] that butadiene and
isoprene in a water acetic acid acetone medium
saturated with sulfur(IV) oxide in the presence of
sodium chloride or HCl and copper(I) chloride react
with diazoaminobenzene and 1-aryl-3,3-dimethyl-1-
triazenes to give chloroarylsulfonylation products.
Proceeding with these studies we established that
activity of the diene system, and this effect compares
with that of the p-nitrophenyl radical [5].
Along with Ia Il, a little aryl chlorides and di-
methylamine hydrochloride are formed.
Most probably, 1-aryl-3,3-dimethyl-1-triazenes first
react with HCl and decompose to give arenediazo-
nium chlorides that then react with unsaturated com-
pounds. Evidence for this suggestion comes from the
fact that for successful reaction of triazenes whose
basicity is decreased the reaction mixture should be
acidified. Thus 1-(p-bromophenyl)- and 1-(p-chloro-
phenyl)-3,3-dimethyl-1-triazenes react in the presence
of conc. HCl only, and 1-(p-nitrophenyl)-3,3-di-
methyl-1-triazene, in the presence of a mixture of
conc. HCl and H SO . At the same time, 1-phenyl-
1
-(m-nitrophenylsulfonyl)- and 1-(p-nitrophenylsul-
fonyl)-1,3-butadienes react with 1-aryl-3,3-dimethyl-
-triazenes in the absence of sulfur(IV) oxide if the
1
reaction mixture contains HCl and copper(I) or cop-
per(II) chloride. The reaction involves expulsion of
the triazene nitrogen and gives rise to 1-(m-nitro-
phenylsulfonyl)- and 1-(p-nitrophenylsulfonyl)-4-aryl-
3
-chloro-1-butenes Ia Il formed by chloroarylation
of the dienes by the double bond most distal from the
arylsulfonyl group (see table).
2
4
and 1-(p-tolyl)-3,3-dimethyl-1-triazenes readily react
in the presence of 10 15% HCl.
1
2
R C H SO CH=CHCH=CH + p-R C H N=NN(CH )
6
4
2
2
6
4
3 2
We have studied reactions of 1-(p-nitrophenylsul-
fonyl)-1,3-butadiene [4], 1-(o-nitrophenylsulfonyl)-,
and 1-(m-nitrophenylsulfonyl)-1,3-butadienes with
arenediazolnium chlorides to find that here, too, 1-(o-
nitrophenylsulfonyl)-1,3-butadiene fails to react, and
its meta and para isomers are chloroarylated to form
the same 1-(m-nitrophenylsulfonyl)-4-aryl-3-chloro-1-
butenes Ia Ie and 1-(p-nitrophenylsulfonyl)-4-aryl-3-
chloro-1-butenes Ig Il.
CuCl
1
2
+
2HCl
R C H SO CH=CHCHClCH C H R -p
6 4 2 2 6 4
+
(CH ) NH HCl + N ,
3 2 2
1
2
R = m-, p-O N, R = H (a), CH (b), Br (c), Cl (d),
2
3
O N (e).
2
The reaction occurs in aqueous acetone at 28 30 C.
-(o-Nitrophenylsulfonyl)-1,3-butadies fail to react
1
It should be noted that with 1-aryl-3,3-dimethyl-1-
triazenes as reagents alternative to arenediazonum
chlorides, the yields of chloroarylation products in-
crease, and the yields of tarry compounds and Sand-
meyer reaction products decrease.
with 1-aryl-3,3-dimethyl-1-triazenes in these condi-
tions, which is probably associated with the fact that
the o-nitrophenylsulfonyl substituent much decreases
the electron density on and, consequently, chemical
The proposed structure of compound Ic is nicely
consistent with its H NMR spectrum that contains
1
1
For communication VIII, see [1].
1
070-3632/05/7504-0580 2005 Pleiades Publishing, Inc.

DIAZO REACTIONS WITH UNSATURATED COMPOUNDS: IX.
581
1
2
Constants, yields, and elemental analyses of chloroarylation products R C H SO CH=CHCHClCH C H R -p
6
4
2
2 6 4
a
Yield, %, in reaction
Found, %
Calculated, %
with
R1
R2
mp,
C
Formula
1
-aryl-3,3- arenedi-
Cl
Cl+Br)
Cl
N
dimethyl-1- azonium
triazenes chlorides
N
(
(Cl+Br)
Ia m-O N H
17
36
30
34
24
49
47
34
35
24
15
42
24
32
23
24
27
29
29
23
73 73.5
111 112
124 125
3.91, 4.05 10.02, 10.12 C H ClNO S
3.98
3.82
10.08
9.69
(26.78)
18.36
8.93
10.08
9.69
(26.78)
18.36
8.93
2
16 14
4
Ib m-O N CH
3.88, 3.96
9.72, 9.78
C H ClNO S
2
3
17 16 4
b
Ic
m-O N Br
3.39, 3.45 (26.85, 26.93) C H BrClNO S 3.25
2
16 13
4
Id m-O N Cl
118 118.5 3.79, 3.85 18.43, 18.50 C H Cl NO S
136.5 137 6.67, 6.98
139.5 140 3.90, 4.11 10.28, 10,32 C H ClNO S
99.5 100 3.94, 4.01
119 199.5 3.36, 3.41 (26.84, 26.93) C H BrClNO S 3.25
132 132.5 3.68, 3.81 18.40, 18.16 C H Cl NO S
152 152.5 7.16, 7.24
3.62
7.06
3.98
3.82
2
16 13
2
4
Ie
m-O N O N
8.59, 8.74
C H ClN O S
2
2
16 13
16 14
2 6
Ig p-O N H
2
4
Ih p-O N CH
9.74, 9.81
C H ClNO S
2
3
17 16 4
Ij
p-O N Br
2
16 13
4
Ik p-O N Cl
3.62
7.06
2
16 13
2
4
Il
p-O N O N
9.14, 9.29
C H ClN O S
2
2
16 13 2 6
a
Compounds Ic Il were purified by crystallization from ethanol and compounds Ia and Ib, from ethanol water, 3:1.
b 1
H NMR spectrum, , ppm: 3.11 3.15 d.d (2H, CH , J 3.3, J 6.9 Hz), 4.62 4.69 d.d (1H, CH, J 6.9, J 13.2 Hz), 6.46 6.51 d
2
1
2
1
2
(
1H, CH, J 15 Hz), 7.00 7.07 m (1H, CH), 7.35 7.38 d.d (4H, p-BrC H ), 7.75 7.80 t (1H, m-O NC H ), 8.07 8.10 d (1H,
6 4 2 6 4
m-O NC H ), 8.48 8.51 d (1H, m-O NC H ), 8.65 s (1H, m-O NC H ).
2
6
4
2
6
4
2
6 4
ethylene proton signals as a well-defined doublet at
.46 6.51 ppm and a multiplet at 7.00 7.07 ppm.
The >CHCl proton signal is a doublet of doublets at
butaene. Yield 6.2 g (45%), light yellow crystals, mp
52 53 C (acetic acid water, 1:1). Found N, %: 5.30,
5.17. C H ClNO S. Calculated N, %: 5.08.
6
1
0
10
4
4
.63 4.69 ppm.
1-(m-Nitrophenylsulfonyl)-1,3-butadiene. A solu-
tion of 2.8 ml of triethylamine in 5 ml of acetone was
added dropwise to a solution of 5.51 g of 1-chloro-4-
(m-nitrophenylsulfonyl)-2-butene in 30 ml of acetone,
cooled with ice water. The mixture was left to stand at
room temperature for 1 h. Triethylamine hydrochlo-
ride precipitated and was separated, the solvent was
removed at reduced pressure, and the solid residue
was recrystallized from ethanol water, 2:1. Yield
3.2 g (76%), light yellow crystals, mp 61 62 C.
Found N, %: 5.76, 5.90. C H NO S. Calculated N,
EXPERIMENTAL
1
The H NMR spectra were obtained on a Varian
VXR-300 spectrometer, solvent CDCl3.
1
-Aryl-3,3-dimethyl-1-triazenes were prepared by
azo coupling of the corresponding arenediazonium
chlorides with dimethylamine [6]. 1-(p-Nitrophenyl-
sulfonyl)-1,3-butadiene was prepared by our prev-
iously described procedure [4].
1
0
9
4
%: 5.55.
1
-Chloro-4-(m-nitrophenylsulfonyl)-2-butene
was prepared similarly to 1-chloro-4-(p-nitrophenyl-
sulfonyl)-2-butene [7] by the reaction of 0.1 mol of
butadiene with the solution of arenediazonium salt,
prepared from 0.05 mol of m-nitroaniline, 17 ml of
conc. HCl, 15 ml of glacial acetic acid, and 3.6 g of
sodium nitrite. Yield 6 g (44%), yellow crystals, mp
Refluxing of 2.4 g of the product with 1 g of
maleic anhydride in 50 ml of benzene for 5 h gave no
adduct.
1-(o-Nitrophenylsulfonyl)-1,3-butadiene was ob-
tained similarly to 1-(m-nitrophenylsulfonyl)-1,3-buta-
diene by the reaction of 5.51 g of 4-chloro-1-(o-nitro-
phenylsulfonyl)-2-butene with 2.8 ml of triethylamine.
Yield 2.96 g (62%), light yellow crystals, mp 79
80 C (ethanol water, 2:1). Found N, %: 5.70, 5.85.
9
5
1 92 C (acetic acid water, 1:1). Found N, %: 5.38,
.12. C H ClNO S. Calculated N, %: 5.08.
1
0
10
4
1
-Chloro-4-(o-nitrophenylsulfonyl)-2-butene
1
was prepared as described above by the reaction of the
solution of arenediazonium salt, prepared from 0.05
mol of o-nitroaniline, 17 ml of HCl, 15 ml of glacial
acetic acid, and 3.6 g of sodium nitrite, with 2.3 l of
C H NO S. Calculated N, %: 5.55. H NMR spec-
1
0
9
4
trum, , ppm: 5.67 5.70 d (1H, CH2, J 9 Hz), 5.76
5.82 d (1H, CH , J 17.1 Hz), 5.41 6.54 m (1H, CH),
2
6.86 6.91 d (1H, CH, J 15 Hz), 7.29 7.31 m (1H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

582
NAIDAN, SMALIUS
CH), 7.76 7.83 m (3H, o-O NC H ), 8.15 8.18 d.d
mixture of 51.2 ml of conc. HCl with 11.2 ml of conc.
2
6
4
(
1H, o-O NC H ).
H SO , and 9.72 g of 3,3-dimethyl-1-(m-nitrophenyl)-
2
6
4
2
4
or 3,3-dimethyl-1-(p-nitrophenyl)-1-triazene.
Refluxing of 2.4 g of the product with 1 g of
maleic anhydride in 50 ml of benzene for 5 h gave no
adduct.
The reactions of 1-(o-nitrophenylsulfonyl)- and
1-(m-nitrophenylsulfonyl)-1,3-butadienes with arene-
diazonium chlorides were performed by a procedure
similar to that described previously for the reactions
of the same chlorides with 1-(p-nitrophenylsulfonyl)-
3
-Chloro-1-(m-nitrophenylsulfonyl)-4-phenyl-1-
butene (Ia) and 3-chloro-1-(p-nitrophenylsulfonyl)-
-phenyl-1-butene (Ig). Acetone, 60 ml, was mixed
4
1,3-butadiene [4] to obtain compounds Ia Id.
with 9.6 g of 1-(m-nitrophenylsulfonyl)-1,3-butadiene
or 1-(p-nitrophenylsulfonyl)-1,3- butadiene, 0.68 g
of copper(II) chloride, and 7.6 g of 3,3-dimethyl-1-
phenyl-1-triazene. The temperature of the reaction
mixture was raised to 30 C, and 20 ml of 15% HCl
was added to it with vigorous stirring. Uniform gas
evolution was observed at 28 30 C. After gas no
longer evolved, the reaction mixture was subjected to
steam distillation to remove acetone and by-products.
The residue was separated and purified by crystalliza-
tion to obtain 2.3 g of compound Ia and 6.9 g of
compound Ig.
REFERENCES
1
2
. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
004, vol. 74, no. 9, p. 1495.
2
. Naidan, V.M., Naidan, G.D., Fesak, O.Yu., Sma-
lius, V.V., Yukhimuk, S.G., Vodop’yan, V.V., and
Goncharenko, D.O., Visn. Cherkas. Univ., Ser. Khim.
Navuk, 2002, no. 30, p. 54.
3. Naidan, V.M. and Smalius, V.V., Abstracts of Papers,
Ukrans’kaya konferents’ya Dombrovs’ki khimihni
chitannya 2003 (Ukrainian Conf. Dombrovskii
Compound Ib was prepared similarly to compound
Ia and compound Ih, similarly to compound Ig.
Chemical Readings 2003 ), Cherkassy, 2003, p. 18.
4
5
6
7
. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
2001, vol. 71, no. 11, p. 1899.
Compounds Ic, Id, Ij, and Ik were prepared
similarly to compounds Ia, Ib, Ig, and Ih, using 10
. Dombrovskii, A.V. and Ganushchak, N.I., Zh. Obshch.
Khim., 1961, vol. 31, no. 6, p. 1896.
. Pochinok, V.Ya., Triazeny (Triazenes), Kiev: Kiev.
Gos. Univ., 1968, pp. 16, 62, 155.
. Naidan, V.M., Naidan, G.D., Drozdova, S.G., and Mu-
sienko, V.M., Zh. Obshch. Khim., 1985, vol. 55, no. 2,
p. 391.
1
9
2 ml of conc. HCl instead of 15% HCl, as well as
.2 g of 1-(p-chlorophenyl)-3,3-dimethyl-1-triazene
and 11.4 g 1-(p-bromophenyl)-3,3-dimethyl-1-triazene,
respectively.
Sulfones Ie and Il were prepared similarly to com-
pounds Ic, Id, Ij, and Im, using, instead of HCl, a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005