Diazo reactions with unsaturated compounds: VI. Reaction of 1-(p-nitrophenylsulfonyl)buta-1,3-diene with arenediazonium chlorides

Article abstract of DOI:10.1023/A:1013963012862

1-(p-Nitrophenylsulfonyl)buta-1,3-diene reacts with arenediazonium chlorides in aqueous acetone in the presence of catalytic amounts of CuCl₂·2H₂O to form 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-bu-tenes. In the presence of SO

Full text of DOI:10.1023/A:1013963012862

Russian Journal of General Chemistry, Vol. 71, No. 11, 2001, pp. 1797 1798. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 11, 2001,
pp. 1899 1901.
Original Russian Text Copyright
2001 by Naidan, Smalius.
Diazo Reactions with Unsaturated Compounds:
VI.1 Reaction of 1-(p-Nitrophenylsulfonyl)buta-1,3-diene
with Arenediazonium Chlorides
V. M. Naidan and V. V. Smalius
Khmel’nitskii Cherkassy State University, Cherkassy, Ukraine
Received May 29, 2000
Abstract 1-(p-Nitrophenylsulfonyl)buta-1,3-diene reacts with arenediazonium chlorides in aqueous acetone
in the presence of catalytic amounts of CuCl2 2H2O to form 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-bu-
tenes. In the presence of SO2, 1-(p-nitrophenylsulfonyl)buta-1,3-diene does not react with arenediazonium
chlorides.
Reactions of 1-arylsulfonylbuta-1,3-dienes with
aromatic diazonium salts were not described in the
literature [1 7]. 1-Phenyl- and 1-( p-tolyl)buta-1,3-di-
enes react with arenediazonium chlorides to give ary-
lation products, whereas 1-( p-nitrophenyl)buta-1,3-
diene is not arylated under the same conditions [8].
not react with arenediazonium chlorides under condi-
tions of chloroarylsulfonylation of unsaturated com-
pounds [9] and was recovered unchanged.
The suggested structure of Ia and Id is nicely con-
1
sistent with their H NMR spectra (Table 2), in which
the ethylene proton signals are well defined and do
not overlap with the signals of other protons. These
signals are doublets and doublets of doublets at 6.83
6.86 and 7.08 7.16 ppm for Ia and at 6.82 6.87 and
We found that 1-( p-nitrophenylsulfonyl)buta-1,3-
diene, in contrast to 1-( p-nitrophenyl)buta-1,3-diene,
reacts with arenediazonium chlorides at 30 C in aque-
ous acetone in the presence of catalytic amounts of 7.07 7.14 ppm for Id. The signal of the >CHCl pro-
CuCl2 2H2O to give 1-( p-nitrophenylsulfonyl)-4-aryl-
3-chloro-1-butenes Ia Ie (Table 1), which are formed
by chloroarylation of the double bond remote from the
arylsulfonyl group.
ton is a doublet of triplets at 5.00 5.07 ppm.
We examined the possibility of dehydrochlorina-
tion of Ia Ie. Experiments showed that the dehydro-
chlorination did occur on heating with KOH in ethan-
ol or with powdered KOH in dioxane, but it was ac-
companied by tarring, probably due to increased activ-
ity toward nucleophiles of the double bond adjacent
to the arylsulfonyl group [10]. Dehydrochlorination of
Ia Ie by heating with triethylamine was incomplete
and yielded a mixture of products which could not be
separated by crystallization.
p-O2NC6H4SO2CH=CH CH=CH2 + p-RC6H4N2Cl
p-O2NC6H4SO2CH=CH CHCl CH2C6H4 R-p + N2
Ia Ie
R = H (a), CH3 (b), Br (c), Cl (d), O2N (e).
The yields of Ia Ie are considerably lower com-
pared to the reactions of arenediazonium chlorides
with 1-phenyl- and 1-( p-tolyl)buta-1,3-dienes [8].
EXPERIMENTAL
Along with Ia Ie, minor amounts of aryl chlorides
are formed. The yields of Ia Ie depend on pH of the
reaction mixture. In the reactions with diazotized ani-
line, p-toluidine, p-bromoaniline, and p-chloroaniline,
the highest yields are attained at pH 4 5, and with
diazotized p-nitroaniline, at pH 1.
1
The H NMR spectra were taken on a Varian VXR-
300 spectrometer (solvent acetone-d6).
1-( p-Nitrophenylsulfonyl)buta-1,3-diene. A 5.51-g
portion of 1-( p-nitrophenylsulfonyl)-4-chloro-2-bu-
tene prepared according to [9] was dissolved in
50 ml of benzene. The solution was cooled with ice-
cold water, and 2.8 ml of triethylamine was added
dropwise. The mixture was refluxed on a water bath
at 70 80 C for 3 h. After cooling, the precipitate of
triethylamine hydrochloride was filtered off, the sol-
The catalyst was introduced in the amount of
0.05 mol per mole of diazonium salt. In the presence
of SO2, 1-( p-nitrophenylsulfonyl)buta-1,3-diene did
*
For communication V, see [1].
1070-3632/01/7111-1797$25.00 2001 MAIK Nauka/Interperiodica

1798
NAIDAN, SMALIUS
Table 1. Constants, yields, and elemental analyses of 1-( p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-butenes Ia Ie
Found, %
Formula
Calculated, %
Cl (Cl + Br)
Comp.
no.
Yield, %
mp,
C
Cl (Cl + Br)
N
N
Ia
Ib
Ic
Id
Ie
47.4
26.8
28.6
28.6
22.5
139.5 140
99.5 100
132 132.5
119 119.5
152 152.5
10.40, 10.21
9.84, 9.91
18.78, 18.54
(27.10, 26.91) 2.96, 3.12 C16H13BrClNO4S
9.10, 9.28 6.78, 6.92 C16H13ClN2O6S
3.71, 3.89 C16H14ClNO4S
3.52, 3.74 C17H16ClNO4S
3.36, 3.71 C16H13Cl2NO4S
10.08
9.69
18.36
(26.78)
8.93
3.98
3.82
3.62
3.25
7.06
Table 2. 1H NMR spectra of 1-(p-nitrophenylsulfonyl)-4-aryl-3-chloro-1-butenes Ia and Id
Comp. no.
, ppm
Ia
3.22 3.35 d.d (2H, CH2, J1 4.2, J2 7.2 Hz), 5.00 5.07 d.t (1H, CH, J1 7.2, J2 7.5 Hz), 6.83 6.88 d
(1H, CH, J 14.5 Hz), 7.08 7.16 d.d (1H, CH, J1 14.5, J2 7.5 Hz), 7.22 7.41 m (5H, C6H5), 8.07 8.11 d
(2H, p-O2NC6H4), 8.44 8.49 d (2H, p-O2NC6H4)
3.24 3.36 d.d (2H, CH2, J1 2.1, J2 7.2 Hz), 4.99 5.07 d.t (1H, CH, J1 7.2, J2 7.8 Hz), 6.82 6.87 d
(1H, CH, J 15 Hz), 7.07 7.14 d.d (1H, CH, J1 7.8, J2 15 Hz), 7.25 7.35 m (4H, p-ClC6H4), 8.07 8.11 d
(2H, p-O2NC6H4), 8.46 8.50 d (2H, p-O2NC6H4)
Id
vent was distilled off at reduced pressure, and the re-
sidue was crystallized from ethanol water, 2 : 1. Yield
4.5 g (95%); light yellow crystals, mp 102 103 C.
Found N, %: 5.88, 5.76. C10H9NO4S. Calculated
N, %: 5.55.
the aromatic amine), constants, and analytical data for
Ia Ie are listed in Table 1.
REFERENCES
1. Naidan, V.M. and Fesak, A.Yu., Zh. Obshch. Khim.,
2000, vol. 70, no. 10, pp. 1702 1704.
Condensation of 1-( p-nitrophenylsulfonyl)buta-
1,3-diene with maleic anhydride. A solution of 2.4 g
of 1-( p-nitrophenylsulfonyl)buta-1,3-diene and 1 g
of maleic anhydride in 50 ml of benzene was heated
for 2 h on a boiling water bath. Then the reaction
mixture was cooled, and the precipitated crystals were
separated and recrystallized from benzene petroleum
ether, 1 : 1. Yield 2.1 g (62.3%); white crystals, mp
134 135 C. Found N, %: 4.16, 4.29. C14H11NO7S.
Calculated N, %: 4.15.
2. Dombrovskii, A.V., Usp. Khim., 1957, vol. 26, no. 6,
pp. 695 715.
3. Dombrovskii, A.V., in Reaktsii i metody issledovaniya
organicheskikh soedinenii (Reactions and Methods for
Investigation of Organic Compounds), Moscow: Gos.
Nauchno-Tekh. Izd. Khimicheskoi Literatury, 1962,
vol. 11, pp. 285 373.
4. Rondestvedt, C.S., Organic Reactions, Adams, R., Ed.,
New York: Wiley, 1944. Translated under the title
Organic Reactions, Moscow: Mir, 1965, coll. 2,
pp. 199 266.
1-( p-Nitrophenylsulfonyl)-4-phenyl-3-chloro-1-
butene Ia. A mixture of 60 ml of acetone, 9.6 g of
1-( p-nitrophenylsulfonyl)buta-1,3-diene, and 1.6 g of
CuCl2 2H2O was heated to 30 C, and a solution of
benzenediazonium chloride, prepared from 3.6 ml of
aniline, 13.6 ml of concentrated HCl, and 2.9 g of
sodium nitrite and neutralized with sodium hydrogen
carbonate to pH 3 4, was added from an externally
cooled dropping funnel with vigorous stirring. Gases
evolved evenly at 30 32 C. After the gas evolution
ceased, the mixture was steam-distilled. The residue
after distillation of acetone and by-products was sep-
arated and crystallized from ethanol. Yield of Ia 6.6 g.
5. Rondestvedt, C.S., Jr., Organic Reactions, New York,
1976, vol. 24, pp. 225 258.
6. Dombrovskii, A.V., Usp. Khim., 1984, vol. 53, no. 10,
pp. 1625 1647.
7. Grishchuk, B.D., Gorbovoi, P.M., Ganushchak, N.I.,
and Dombrovskii, A.V., Usp. Khim., 1994, vol. 63,
no. 3, pp. 269 279.
8. Dombrovskii, A.V. and Ganushchak, N.I., Zh. Obshch.
Khim., 1961, vol. 31, no. 6, pp. 1896 1901.
9. Naidan, V.M., Naidan, G.D., Drozdova, S.G., and
Musienko, V.M., Zh. Obshch. Khim., 1985, vol. 55,
no. 2, pp. 391 395.
10. Sykes, P., A Guidebook to Mechanism in Organic
Chemistry, New York: Longman, 1986. Translated
under the title Mekhanizmy reaktsii v organicheskoi
khimii, Moscow: Khimiya, 1977, p. 193.
Compounds Ib Ie were prepared similarly to Ia
and crystallized from ethanol. The yields (based on
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 11 2001