Diazo reactions with unsaturated compounds: XII. Reaction of 1-(p-Carboxybenzenesulfonyl)-1,3-butadiene with aryldiazonium chlorides, 1-aryl-3,3-dimethyl-1-triazenes, and aryldiazonium tetrachlorocuprates(II)

Article abstract of DOI:10.1134/S1070363207040147

1-(p-Carboxybenzenesulfonyl)-1,3-butadiene reacts in aqueous acetone with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-1-triazenes in the presence of copper(II) chloride and with tetrachlorocuprates(II) to form 1-(p-carboxybenzenesulfonyl)-4-aryl-3-chloro-1-butenes. Nauka/Interperiodica 2007.

Full text of DOI:10.1134/S1070363207040147

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 4, pp. 586 588.
Pleiades Publishing, Ltd., 2007.
Original Russian Text V.V. Smalius, V.M. Naidan, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 4, pp. 627 629.
Diazo Reactions with Unsaturated Compounds:
1
XII. Reaction of 1-(p-Carboxybenzenesulfonyl)-1,3-butadiene
with Aryldiazonium Chlorides, 1-Aryl-3,3-dimethyl-1-triazenes,
and Aryldiazonium Tetrachlorocuprates(II)
V. V. Smalius and V. M. Naidan
Bogdan Khmel’nitskii Cherkassy National University,
bul’v. Shevchenko 81, Cherkassy, 18031 Ukraine
Received October 31, 2006
Abstract 1-(p-Carboxybenzenesulfonyl)-1,3-butadiene reacts in aqueous acetone with aryldiazonium
chlorides and 1-aryl-3,3-dimethyl-1-triazenes in the presence of copper(II) chloride and with tetrachlorocup-
rates(II) to form 1-(p-carboxybenzenesulfonyl)-4-aryl-3-chloro-1-butenes.
DOI: 10.1134/S1070363207040147
We have shown previously [1 3] that 1-(p-nitroben-
zenesulfonyl)-, 1-(m-nitrobenzenesulfonyl)-, 1-(p-chlo-
In this study we found that 1-(p-carboxybenzene-
sulfonyl)-1,3-butadiene reacts similarly with aryldia-
zonium chlorides and tetrachlorocuprates(II) and with
1-aryl-3,3-dimethyl-1-triazene to form 1-(p-carboxy-
benzenesulfonyl)-4-aryl-3-chloro-1-butenes Ia Ie (see
table), the products of chloroarylation of the double
bond remote from the arenesulfonyl group.
robenzenesulfonyl)-,
1-(p-bromobenzenesulfonyl)-,
1-(p-methylbenzenesulfonyl)-, and 1-(p-methoxyben-
zenesulfonyl)-1,3-butadienes react with aryldiazonium
chlorides and 1-aryl-3,3-dimethyl-1-triazenes to give
the corresponding chloroarylation products.
p-HOOCC H SO CH=CH CH=CH
2
6
4
2
p-RC H N Cl
(p-RC6H4N2)2CuCl4
6
4 2
p-HOOCC H SO CH=CH CHCl CH C H R-p
6
4
2
2
6 4
N2
N2
Ia Ie
N ,
2
(
CH ) NH HCl
3 2
p-HOOCC H SO CH=CH CH=CH + p-RC6H4N=NN(CH3)2 + 2HCl,
6
4
2
2
R = H (a), CH (b), Br (c), Cl (d), O N (e).
3
2
The reaction with aryldiazonium tetrachlorocup-
rates(II) occurs in aqueous acetone at 32 34 C, and
with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-
azene, dimethylamine hydrochloride is additionally
obtained. Most probably, 1-aryl-3,3-dimethyl-1-tria-
zenes in the first step react with hydrochloric acid to
give aryldiazonium chlorides, which subsequently
react with the diene.
1
-triazenes it occurs under the similar conditions in
the presence of copper(II) chloride. In the reaction
with 1-aryl-3,3-dimethyl-1-triazene, hydrochloric acid
was added to the reaction mixture.
Aryldiazonium tetrachlorocuprates(II) react with
1
-(p-carboxybenzenesulfonyl)-1,3-butadiene to form
Along with compounds Ia Ie, aryl chlorides are
formed, and in the case of 1-aryl-3,3-dimethyl-1-tri-
products Ia Id in a higher yield as compared to their
yields from 1-aryl-3,3-dimethyl-1-triazenes. The
lowest yields of Ia Ie are observed in the reaction of
1
-( p-carboxybenzenesulfonyl)-1,3-butadiene with
1
For communication XI, see [1].
aryldiazonium chlorides.
586

DIAZO REACTIONS WITH UNSATURATED COMPOUNDS: XII.
587
Constants, yields, and elemental analyses of the products of chloroalkylation of 1-( p-carboxybenzenesulfonyl)-1,3-buta-
diene p-HOOC C H SO CH=CH CHCl CH C H R-p
6
4
2
2 6 4
Yield, %
reactions
with
aryldiazonium
tetrachloro-
cuprates
Comp.
no.
reactions
with
aryldiazonium
chlorides
R
reactions
with
triazenes
mp, C
Found, %
Formula
Calculated, %
a
Ia
H
52
40
33
55
49
39
58
60
47
159 160 Cl 10.34, 10.02 C H ClO S
Cl 0.10
Cl 9.71
1
7
15
4
Ib CH3
Ic Br
177 178 Cl 9.91, 9.50
C H ClO S
18 17 4
193 194 (Cl+Br) 27.13, C H BrClO S (Cl+Br) 26.84
1
7
14
4
2
6.52
Id Clb
Ie O N
47
28
52
32
56
191 192 Cl 18.78, 18.11 C H Cl O S Cl 18.40
197 198 N 3.28, 3.33
Cl 8.90, 8.85
1
7
14
2 4
C H ClNO S N 3.53
2
17 14 6
Cl 8.95
a
b 1
1
1
7
-Aryl-3,3-dimethyl-1-triazenes.
H NMR spectrum, , ppm: 3.117 3.258 m (2H, CH ), 4.080 5.025 d.d (1H, CH, J 7.2, J
2 1 2
4.4 Hz), 6.856 6.893 d (1H, CH, J 14.8 Hz), 6.959 7.015 d.d (1H, CH, J 7.6, J 14.8 Hz), 7.196 7.245 t (4H, p-ClC H ), 7.852
.873 d (2H, p-O NC H ), 8.142 8.163 d (2H, p-O NC H ), 13.40 13.65 s (1H, COOH).
1
2
6 4
2
6
4
2
6 4
The suggested structure of Id well agrees with its
H NMR spectrum. The ethylene protons give a
doublet at 6.856 5.893 ppm and a doublet of doub-
lets at 6.959 7.015 ppm. The signal of the >CHCl
proton is manifested as a doublet of doublets at 4.949
.025 ppm. Large coupling constants (J 14.8 Hz) of
the ethylene protons are indicative of their trans
arrangement in Id.
was added in small portions. The reaction mixture was
heated on a water bath at 80 C for 2 h. The triethyl-
amine hydrochloride precipitate was filtered off, and
the benzene solution of the diene was evaporated at
reduced pressure. The oily residue was treated with
stirring with 16 ml of 10% HCl. The precipitate ob-
tained was separated and crystallized from a 1:2
ethanol water mixture to give 11 g (92.3%) of a white
crystalline substance, mp 174 175 C. Found, %: S
13.20, 13.78. C H O S. Calculated, %: S 13.45.
1
5
EXPERIMENTAL
1
1
10
4
1
All the attempts to obtain the adduct of this diene
with maleic anhydride failed. The reaction mixture
underwent tarring in the course of heating of an ace-
tone or dioxane solution of the reactants.
The H NMR spectra were taken on a Varian
Gemini-400 spectrometer in DMSO-d6.
1
-Aryl-3,3-dimethyl-1-triazenes were prepared by
azo coupling of the corresponding aryldiazonium
chlorides with dimethylamine [4].
1-(p-Carboxybenzenesulfonyl)-4-aryl-3-chloro-1-
butenes Ia Ie. a. To a mixture of 75 ml of acetone,
Aryldiazonium tetrachlorocuprates(II) were pre-
pared according to [5].
10 ml of water, 2 g of copper(II) chloride, and 11.91 g
of 1-(p-carboxybenzenesulfonyl)-1,3-butadiene,
solution of aryldiazonium chloride prepared from
.05 mol of appropriate aromatic amine, 17 ml of
a
1
-( p-Carboxybenzenesulfonyl)-4-chloro-2-bu-
0
tene was prepared similarly to 1-(p-nitrobenzenesul-
fonyl)-4-chloro-2-butene [6]. Butadiene, 0.1 mol,
reacted with a diazonium salt solution prepared from
concentrated hydrochloric acid, and 3.6 g of sodium
nitrite was added dropwise with stirring at 32 34 C.
The solutions of phenyl-, p-tolyl-, p-chlorophenyl-,
and p-bromophenyldiazonium chlorides were prelim-
inarily neutralized with sodium bicarbonate to pH
0
.05 mol of p-aminobenzoic acid to give 5.8 g (42%)
of a white crystalline substance, mp 202 203 C (from
:2 ethanol water). Found, %: Cl 12.76, 12.84.
C H ClO S. Calculated, %: Cl 12.90.
1
3
4. After the addition of the diazonium salt solution
1
1
11
4
was complete, the reaction mixture was stirred until
liberation of gaseous products ceased and then was
poured into 400 ml of water. The crystalline precip-
itate was separated and recrystallized from a 1:2
acetic acid water mixture.
1
-( p-Carboxybenzenesulfonyl)-1,3-butadiene.
To a solution of 0.05 mol of 1-(p-carboxybenzenesul-
fonyl)-4-chloro-2-butene in 130 ml of benzene, a solu-
tion of 0.1 mol of triethylamine in 20 ml of benzene
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 4 2007

588
SMALIUS, NAIDAN
b. To the mixture described above (procedure a),
.063 mol of appropriate aryldimethyltriazene was
REFERENCES
0
added. After that, in the syntheses of Ia and Ib, 30 ml
of 15% hydrochloric acid was added dropwise with
stirring. In the case of Ic and Id, the reaction mixture
was treated with 15 ml of concentrated hydrochloric
acid. When preparing Ie, a mixture of 64 ml of con-
centrated hydrochloric acid and 14 ml of concentrated
sulfuric acid was used. The temperature of the reac-
tion mixture was maintained in the range 32 34 C.
The target products were isolated as in procedure a.
1. Smalius, V.V. and Naidan, V.M., Zh. Obshch. Khim.,
2
006, vol. 76, no. 8, p. 1350.
. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
001, vol. 71, no. 11, p. 1899.
. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
005, vol. 75, no. 4, p. 619.
2
3
2
2
4. Pochinok, V.Ya., Triazeny (Triazenes), Kiev: Kiev.
Gos. Univ., 1968, pp. 16, 62, 155.
c. A mixture of 100 ml of acetone, 25 ml of water,
1
1.91 g of 1-(p-carboxybenzenesulfonyl)-1,3-buta-
5
6
. Obushak, N.D., Lyakhovich, M.B., and Bilaya, E.E.,
Zh. Org. Khim., 2002, vol. 38, no. 1, p. 47.
diene, and 0.025 mol of appropriate aryldiazonium
tetrachlorocuprate(II) was vigorously stirred at 32
. Naidan, V.M., Naidan, G.D., Drozdova, S.G., and Mu-
sienko, V.M., Zh. Obshch. Khim., 1985, vol.55, no. 2,
p. 391.
3
4 C until the liberation of gaseous products ceased.
The reaction products were isolated similarly to
methods a and b.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 4 2007