DIAZO REACTIONS WITH UNSATURATED COMPOUNDS: XI.
1297
fonyl)-2-butene [4] by the reaction of 2.3 l of buta-
diene with a solution of diazonium salt, prepared
from 4.5 ml of aniline, 17 ml of conc. HCl, and 3.6 g
of sodium nitrite and neutralized to pH 3 4 with
NaHCO3. When gaseous products no longer evolved,
the reaction mixture was poured into 300 ml of water,
and the organic layer was treated with ether. The
ethereal extract was washed with water and dried with
Na2SO4. The ether was then removed, and the residue
was distilled in a vacuum to obtain 4.9 g (43%) of
amine hydrochloride). Melts at room temperature.
Found S, %: 15.20, 15.25. C10H12O2S. Calculated S,
%: 15.39.
1-( p-Methoxylbenzenesulfonyl)-1,3-butadiene
was prepared and isolated in a similar way by the re-
action of 13.03 g of 4-chloro-1-(p-methoxylbenzene-
sulfonyl)-2-butene with 6.9 ml of triethylamine. Yield
83% (based on triethylamine hydrochloride). Melts at
room temperature. Found S, %: 14.02, 14.16. C11H12
O3S. Calculated S, %: 14.29.
2
a light yellow liquid, bp 140 144 C (10 mm Hg),
n2D0 1.5590 [6].
3-Chloro-1-(p-methylbenzenesulfonyl)-4-phenyl-
1-butene (Ia). a. Copper(I) chloride, 0.85 g, and 9.5 g
of 3,3-dimethyl-1-phenyl-1-triazene were added to an
acetone solution of 1-(p-methylbenzenesulfonyl)-1,3-
butadiene prepared as described above from 12.23 g
of 4-chloro-1-( p-methylbenzenesulfonyl)-2-butene.
The reaction mixture was heated to 30 C, after which
25 ml of 15% HCl was added with vigorous stirring
so that gaseous products evolved evenly. The tem-
perature of the reaction mixture was maintained at
30 32 C. After the addition of HCl had been com-
plete, the reaction mixture was stirred until gases no
longer evolved and then poured into 400 ml of water.
The crystals that formed were separated and crystal-
lized from ethanol water, 2:1.
4-Chloro-1-(p-methylbenzenesulfonyl)-2-butene
was prepared in a similar way by the reaction of a
solution of diazonium salt prepared from 5.35 g of
p-toluidine, 17 ml of conc. HCl, and 3.6 g of sodium
nitrite, neutralized to pH 3 4 with NaHCO3, with 2.3 l
of butadiene. When gaseous products no longer
evolved, the reaction mixture was poured into 400 ml
of water. A precipitate formed and was separated and
crystallized from ethanol water, 1:1, to obtain 3.3 g
(27% ) of colorless crystals, mp 66 67 C. Found Cl,
%: 14.26, 14.30. C11H13ClO2S. Calculated Cl, %:
14.48.
4-Chloro-1-( p-methoxylbenzenesulfonyl)-2-
butene was prepared similarly to 4-chloro-1-(p-me-
thylbenzenesulfonyl)-2-butene by the reaction of a
solution of arenediazonium salt prepared from 6.15 g
of p-anisidine, 17 ml of conc. HCl, and 3.6 g of
sodium nitrite with 2.3 l of butadiene. Yield 2.7 g
(21% ), colorless crystals, mp 61 61.5 C (from acetic
acid water, 1:2). Found Cl, %: 13.42, 13.54.
C11H13ClO3S. Calculated Cl, %: 13.59.
b. Copper(II) chloride, 2 g, was added to an ace-
tone solution of 1-(p-methylbenzenesulfonyl)-1,3-
butadiene prepared as described in procedure a. A
solution of benzenediazonium chloride prepared from
4.55 ml of aniline, 17 ml of conc. HCl, and 3.6 g
sodium nitrite, neutralized to pH 3 4 with NaHCO3,
was then added with vigorous stirring. The reaction
mixture was stirred until gases no longer evolved. The
products were isolated as described in procedure a.
1-(Benzenesulfonyl)-1,3-butadiene. A solution of
6.9 ml of triethylamine in 10 ml of acetone was added
in small portions to a solution of 11.52 g of 4-chloro-
1-(benzenesulfonyl)-2-butene in 50 ml of acetone.
A precipitate of triethylamine hydrochloride formed.
The reaction mixture was allowed to stand for 30 min
at room temperature, the precipitate was filtered off,
and the acetone solution was poured into 400 ml of
water. The oily material that formed was crystallized
from hexane under dry ice cooling. Yield 73% (besed
on triethylamine hydrochloride). Melts at room tem-
perature [4]. Found S, %: 16.32, 16.41. C10H10O2S.
Calculated S, %: 16.50.
3-Chloro-1-( p-methoxylbenzenesulfonyl)-4-
phenyl-1-butene (If) was prepared similarly to com-
pound Ia from 1-(p-methoxylbenzenesulfonyl)-1,3-
butadiene obtained by dehydrochlorination of 13.03 g
of 4-chloro-1-( p-methoxylbenzenesulfonyl)-2-butene
with triethylamine, like with 1-(p-methylbenzenesul-
fonyl)-1,3-butadiene.
Compounds Ib, Ic, Id, Ig, Ih, and Ij were prepared
similarly to Ia, using 15 ml of conc. HCl instead of
15% HCl, and 11.5 g of 1-(p-chlorophenyl)-3,3-di-
methyl-1-triazene and 14.25 g of 1-(p-bromophenyl)-
3,3-dimethyl-1-triazene, respectively.
1-(p-Methylbenzenesulfonyl)-1,3-butadiene was
prepared similarly to 1-(benzenesulfonyl)-1,3-butadi-
ene by the reaction of 12.23 g of 4-chloro-1-(p-me-
thylbenzenesulfonyl)-2-butene with 6.9 ml of tri-
ethylamine and isolated by crystallization from hexane
under dry ice cooling. Yield 87% (besed on triethyl-
Sulfones Ie and Ik were prepared similarly to Ic,
Id, Ih, and Ij, using a mixture of 64 ml of conc. HCl
and 14 ml of conc. H2SO4 instead of conc. HCl.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006
Smalius
