Diazo reactions with unsaturated compounds: X. Reactions of p-chloro- and p-bromophenysulfonyl-1,3-butadienes with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-1-triazenes

Article abstract of DOI:10.1007/s11176-005-0508-3

1-(p-Chlorophenylsulfonyl)- and 1-(p-bromophenylsulfonyl)-1,3-butadienes in aqueous acetone solutions in the presence of cuprous chloride or cupric chloride react with aryldiazonium chlorides and 1-aryl-3,3-dimethyl-1-triazenes to form 1-(p-chlorophenylsu

Full text of DOI:10.1007/s11176-005-0508-3

Russian Journal of General Chemistry, Vol. 75, No. 11, 2005, pp. 1771 1773. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 11, 2005,
pp. 1854 1856.
Original Russian Text Copyright
2005 by Naidan, Smalius.
Diazo Reactions with Unsaturated Compounds:
X.1 Reactions of p-Chloro-
and p-Bromophenysulfonyl-1,3-Butadienes with Aryldiazonium
Chlorides and 1-Aryl-3,3-dimethyl-1-triazenes
V. M. Naidan and V. V. Smalius
Khmelnitskii National University, Cherkassy, Ukraine
Received November 23, 2004
Abstract 1-(p-Chlorophenylsulfonyl)- and 1-(p-bromophenylsulfonyl)-1,3-butadienes in aqueous acetone
solutions in the presence of cuprous chloride or cupric chloride react with aryldiazonium chlorides and 1-aryl-
3,3-dimethyl-1-triazenes to form 1-(p-chlorophenylsulphonyl)- and 1-(p-bromophenylsulfonyl)-4-aryl-3-chloro-
1-butenes, respectively.
Earlier [1,2] it was shown that 1-(p-nitrophenylsul-
fonyl)- and 1-(m-nitrophenylsulfonyl)-1,3-butadienes
react with aryldiazonium chlorides and 1-aryl-3,3-
dimethyl-1-triazenes to give the corresponding pro-
ducts of chloroarylation.
dimethylamine hydrochloride are formed. The yields
of compounds (Ia Ik) are practically not dependent
on the nature of the substituent in the benzene ring of
the arylsulfonyl radical (see the table).
Taking 1-aryl-3,3-dimethyl-1-triazenes as agents
alternative to aryldiazonium chlorides in this reaction
results in the increased yields of products of chloro-
arylation, lower yields of gummy products, and the
products of the Sandmeyer’s reaction.
In the present study it was found that 1-(p-chloro-
phenylsulfonyl)- and 1-(p-bromophenylsulfonyl)-1,3-
butadienes behave in the reaction of chloroarylation
in a similar way.
The attempts to obtain the products of the reaction
of 1-(p-chloropenylsulfonyl)- and 1-(p-bromophenyl-
sulfonyl)-1,3-butadienes with maleic anhydride were
not successful. On heating the acetone solutions of
these dienes and maleic anhydride, the reaction mix-
ture completely resinifies.
R1C6H4SO2CH=CH CH=CH2 + p-R2C6H4N2Cl
R1C6H4SO2CH=CH CHCl CH2C6H4R2-p + N2
The proposed structure of compounds Id and Ik is
in conformity with the data of their H NMR spectra
in which there are clearly observed ethylene protons
manifesting themeselves as a doublet at 6.377
6.431 ppm for compound Id and double doublet at
6.944 7.014 ppm for compound Ik.
(CH3)2NH HCl
1
R1C6H6SO2CH=CH CH=CH2 + p-R2C6H4N=NN(CH3)2
+ 2HCl,
R1 = p-Cl, p-Br; R2 = H (a, f), CH3 (b, g), Br (c, h), Cl
(d, j), O2N (e, k).
The signal of the proton of the >CHCl group ap-
pears as a double doublet at 4.555 4.621 ppm for
compound Id, and as a double doublet at 4.665
4.729 ppm for compound Ik.
Reactions of both aryldiazonium chlorides and
1-aryl-3,3-dimethyl-1-triazenes take place in aqueous
acetone solution in the presence of either cuprous, or
cupric chloride at 28 30 C.
In the presence of sulfur dioxide neither 1-(p-
chlorophenylsulfonyl)-, nor 1-(p-bromophenylsul-
fonyl)-1,3-butadienes under the conditions of the re-
action of chlorosulfonylation enter the reaction with
either aryldiazonium chlorides, or 1-aryl-3,3-dimethyl-
triazenes.
Along with compounds (Ia-Ik), aryl chlorides, and
in the reaction with 1-aryl-3,3-dimethyltriazenes also
1
For communication IX , see [1].
1070-3632/05/7511-1771 2005 Pleiades Publishing, Inc.

1772
NAIDAN, SMALIUS
Constants, yields, and elemental analyses of the products of chloroarylation of 1-(p-chlorophenylsulfonyl)- and 1-(p-
bromophenylsulfonyl)-1,3-butadienes
Yield, %
Comp.
mp,
C
Found, %
Formula
Calculated, %
no. a
b
c
IIa
IIb
IIc
42
44
44
45
31
10
34
38
39
26
61 61.5
110 110.5 Cl
98 98.5
89.5 90
145 146
Cl
20.54, 20.68
20.03, 20.10
Cl + Br 35.60, 35.75
C16H14Cl2O2S
C17H16Cl2O2S
C16H13BrCl2O2S Cl + Br 35.89
C16H13Cl3O2S
C16H13Cl2NO4S
Cl
Cl
20.77
19.95
IIdd
IIe
Cl
N
28.14, 28.25
3.63, 3.65
Cl
N
28.31
3.62
Cl
18.31, 18.36
Cl
18.35
IIf
IIg
IIh
IIi
42
48
41
43
31
9.5
38
35
36
37
89 90
118 119
Cl + Br 29.82, 29.88
Cl + Br 28.64, 28.75
C16H14BrClO2S
C17H16BrClO2S
C16H13Br2ClO2S Cl + Br 42.02
C16H13BrCl2O2S Cl + Br 35.89
Cl + Br 29.90
Cl + Br 28.85
112 112.5 Cl + Br 42.17, 42.22
101 102
150 151
Cl + Br 35.82, 35.90
3.17, 3.24
Cl + Br 26.63, 26.71
Ije
N
C16H13BrClNO4S
N
3.25
Cl + Br 26.78
a
b
Compounds Ia Ik were purified by crystallization from an ethanol-water mixture, 3:1. Reaction with 1-aryl-3,3-dimethyl-1-tri-
azenes. Reaction with aryldiazonium chlorides.
c
d 1
H NMR spectrum, ppm: 3.077 3.108 d.d (2H, CH , J 2.4, J 6.9 Hz), 4.555
2 1 2
4.621 d.d (1H, CH, J 6.0, J 13.5 Hz), 6.377 6.431 d.d (1H, CH, J 1.2, J 15.3 Hz), 6.865 6.936 d.d (1H, CH, J 6.6, J 2.4 Hz),
1
2
1
2
1
2
7.021 7.049 d (2H, p-ClC6H4, J 8.4 Hz), 7.189 7.218 d (2H, p-ClC6H4, J 2.7 Hz), 7.465 7.494 d (2H, p-ClC6H4, J 8.7 Hz),
e 1
7.665 7.693 d (2H, p-ClC6H4, J 8.4 Hz). H NMR spectrum, ppm: 3.167 3.328 m (2H, CH ), 4.665 4.729 d.d (1H, CH, J 6.6,
2
1
J 12.9 Hz), 6.492 6.541 d (1H, CH, J 11.7 Hz), 6.944 7.014 d.d (1H, CH, J 6.3, J 14.4 Hz), 7.319 7.348 d (2H, p-O2NC6H4, J
2
1
2
8.7 Hz), 7.615 7.860 m (4H, p-BrC6H4), 8.123 8.151 d (2H, p-O2NC6H4, J 8.4 Hz).
EXPERIMENTAL
The H NMR spectra were obtained on a Varian
VXR-300 spectrometer with CDCl3 as a solvent.
1-(p-Chlorophenylsulfonyl)-1,3-butadiene.
1-(p-Chlorophenylsulfonyl)-4-chloro-2-butene,
13.25 g, was dissolved in 50 ml of acetone. To this
solution a solution of 6.9 ml of triethylamine in 10
ml of acetone was added by small portions. The reac-
tion mixture was kept at room temperature for 30 min,
the formed precipitate of triethylammonium chloride
was filtered off, and the acetone solution of the ob-
tained diene was poured into 400 ml of water. The
formed oily substance crystallized on cooling with an
ice-sodium chloride mixture from 16 to 18 C. The
obtained crystalline product was separated and re-
crystallized from an ethanol water (1:1) mixture or
from petroleum ether. We obtained 6.0 g of a light
yellow crystalline substance which melts at room
temperature. Found Cl, %: 15.12, 15.20. C10H9ClO2S.
Calculated Cl, %: 15.50.
1
1-Aryl-3,3-dimethyl-1-triazenes were prepared
by azo coupling of the corresponding aryldiazonium
chlorides with dimethylamine [4].
1-(p-Chlorophenylsulfonyl)-4-chloro-2-butene
was prepared similarly to that described for 1-(p-nitro-
phenylsulfonyl)-4-chloro-2-butene [3]. By the reaction
of 2.3 ml of butadiene with a solution of the diazo-
nium salt prepared from 6.38 g of p-chloroaniline,
17 ml of conc. HCl, 3.6 g of sodium nitrite and then
neutralized with NaHCO3 to pH 3 4 we obtained
5.8 g of a yellow crystalline substance with a mp of
68 C (ethanol water, 1:1). Found Cl, %: 26.70, 26.84.
C10H10Cl2O2S. Calculated Cl, 18:18:57%: 26.74.
1-(p-Bromophenylsulfonyl)-1,3-butadiene
was
1-(p-Bromophenylsulfonyl)-4-chloro-2-butene
was prepared similarly by the reaction of a neutralized
with NaHCO3 to pH 3 4 solution of a diazonium salt
(from 8.6 g of p-bromoaniline, 17 ml of conc. HCl,
3.6 g of sodium nitrite) with 2.3 ml of butadiene. We
isolated 6.7 g (43%) of a light yellow substance, mp
82 82.5 C (acetic acid water, 1:1). Found Cl + Br,
%: 37.56, 37.64. C10H10BrClO2S. Calculated Cl + Br,
%: 37.62.
obtained by the reaction of 15.47 g of 1-(p-bromo-
phenylsulfonyl)-4-chloro-2-butene with 6.9 ml of tri-
ethylamine. We isolated 9.3 g (69%) of a light yellow
substance, mp 44 45 C (ethanol water, 1:1 or petro-
leum ether). Found Br, %: 28.82, 28.95. C10H9BrO2S.
Calculated Br, %: 29.25.
1-(p-Chlorophenylsulfonyl)-4-phenyl-3-chloro-1-
butene (Ia). a. An acetone solution of 1-(p-chloro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

DIAZO REACTIONS WITH UNSATURATED COMPOUNDS: X.
1773
phenylsulfonyl)-1,3-butadiene prepared as described
above from 13.25 g of 1-(p-chlorophenylsulfonyl)-4-
chloro-2-butene was transferred into a three-necked
flask, and to the solution 0.85 g of cuprous chloride
and 9.5 g of 1-(p-phenyl-3,3-dimethyl-1-triazene were
added. The temperature of the reaction mixture was
raised to 30 C, and 25 ml of 15% hydrochloric acid
was added dropwise with vigorous stirring at such a
rate that steady liberation of gaseous products was
going on. Over the course of addition of hydrochloric
acid the temperature of the reaction mixture was
maintained within the interval of 28 30 C by external
cooling. After addition of hydrochloric acid the
reaction mixture was further stirred until the liberation
of gaseous products ceased. After the completion of
the reaction the contents of the flask was poured into
400 ml of water, the formed crystalline substance was
separated and purified by recrystallization from an
ethanol water (3:1) mixture.
for Ia with 1-(p-bromophenylsulfonyl)-1,3-butadiene
instead of 1-(p-chlophenylsulfonyl)-1,3-butadiene.
The former diene was prepared by dehydrochlorina-
tion of 15.47 g of 1-(p-bromophenylsufonyl)-4-chloro-
2-butene with triethylamine, as described above for
the preparation of 1-(p-chlorophenylsulfonyl)-1,3-
butadiene.
Compounds Ib and Ig were prepared similarly to
that described for Ia.
Compounds Ic, Id, Ih, and Ij were prepared
similarly to compound Ia taking into the reaction
15 ml of conc. HCl instead of 15% HCl from 11.5 g
of 1-(p-chlorophenyl)-3,3-dimethyl-1-triazene and
14.25 g of 1-(p-bromophenyl)-3,3-dimethyl-1-triazene,
respectively.
Sulfones Ie and Ik were prepared similarly to
compounds Ic, Id, Ih, and Ij taking into the reaction a
mixture of 64 ml of conc. HCl and 14 ml of conc.
H2SO4 instead of hydrochloric acid and 12.15 g of
1-(p-nitrophenyl)-3,3-dimethyl-1-triazene.
b. To an acetone solution of 1-(p-chlorophenyl-
sulfonyl)-1,3-butadiene prepared as described above
in a 2.0 g of cupric chloride was first added, and then
a neutralized with NaHCO3 to pH 3 4 solution of
phenyldiazonium chloride prepared from 4.55 ml of
aniline, 17 ml of conc. HCl, and 3.6 g of sodium
nitrite was added dropwise with vigorous stirring.
Over the course of addition of the diazonium salt the
temperature of the reaction mixture was kept within
the interval of 28 30 C. After the addition of the
diazonium salt the reaction mixture was further stirred
to the complete end of liberation of gaseous products.
After the completion of the reaction the products were
isolated by the same method as described above in a.
REFERENCES
1. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
2005, vol. 75, no. 4, p. 619
2. Naidan, V.M. and Smalius, V.V., Zh. Obshch. Khim.,
2001, vol. 71, no. 11, p. 1899
3. 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-(p-Bromophenylsulfonyl)-4-phenyl-3-chloro-1-
butene (If) was prepared similarly to that described
4. Pochinok, V.Ya., Triazeny (Triazenes), Kiev: Kiev
State Univ., 1968, pp. 16, 62, 155.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005