440
GATAULLIN et al.
the reacted amine V) of dialkenylaniline I, bp 140
45 C (2 mm Hg).
as an amorphous mass; yield 0.51 g (95%), R 0.4
f
1
(eluent CH Cl ).
2 2
6
-Methyl-4-(1-methyl-2-buten-1-yl)-2-(1-cyclo-
N-Tosyl-6-(1-methyl-2-buten-1-yl)-3,4,4a,9a-tet-
rahydrocarbazole XIII. A solution of 0.377 g of
hexen-1-yl)aniline II was prepared similarly to I by
procedure (a) from 1 g of XI; yield 1.19 g (87%).
1-iodohexahydrocarbazole XII in 3 ml of piperidine
was heated at 110 C for 3 h. After the dehydroiodina-
tion completion, the solvent was vacuum-evaporated,
and the residue was dissolved in 50 ml of CH Cl and
N-Tosyl-6-methyl-4-(1-methylbut-2-en-1-yl)-2-(2-
cyclohexen-1-yl)aniline X. To a solution of 1.27 g
of amine I in 10 ml of pyridine was added 1.7 g of
p-toluenesulfonyl chloride. The mixture was allowed
2
2
washed with water (2 20 ml). The organic phase
was dried over Na SO , and the solvent was vacuum-
2
4
to stand at room temperature for 24 h, 0.5 ml of H O
2
evaporated; yield of XIII 0.26 g (90%), R 0.7 (eluent
f
was added, the mixture was stirred for 30 min, and the
solvent was vacuum-evaporated. The residue was
diluted with 5 ml of H O and 50 ml of CH Cl . The
organic phase was separated, washed with 30 ml of
% HCl and water (2 10 ml), and dried over MgSO4.
After vacuum evaporation of the solvent, 2 g of crude
X was obtained; the product slowly solidified in air
and was sufficiently pure for the subsequent syntheses.
Recrystallization from EtOH gave 0.63 g of crystal-
line X, mp 124 126 C (from EtOH). An additional
CH Cl ).
2
2
2
2
2
CONCLUSIONS
5
(1) Alkenylation of 6-methyl-2-(2-cyclohexen-1-
yl)- and -2-(1-cyclohexen-1-yl)anilines with piperyl-
ene in the presence of AlCl gives the corresponding
3
4-(1-methyl-2-buten-1-yl)anilines in 87 88% yields.
(2) The reaction of the synthesized 6-methyl-2-(2-
cyclohexen-1-yl)-4-(1-methyl-2-buten-1-yl)aniline
0
.4-g crop of X was obtained from the mother liquor
after its prolonged storage; mp 126 130 C.
with I gave iodohexahydrocarbazole in 95% yield.
2
On refluxing in piperidine, it transformed into the
tetrahydrocarbazole in 90% yield.
6
-Methyl-2-(1-cyclohexen-1-yl)aniline XI. 6-Me-
thyl-2-(2-cyclohexen-1-yl)aniline (10 g) [3] and KOH
10 g) were heated for 1 h on a silicone bath (300 C)
(
REFERENCES
in a steel test tube equipped with a reflux air condens-
er. After cooling, the product was decanted from KOH
and vacuum-distilled. Yield 9.5 g (95%), bp 118
1
2
. Narasimhan, N.S. and Gokhale, S.M., J. Indian Inst.
Sci., 2001, vol. 81, no. 2, pp. 135 138.
. Mustafin, A.G., Khalilov, I.N., Sharafutdinov, V.M.,
et al., Izv. Ross. Akad. Nauk, Ser. Khim., 1997, no. 3,
pp. 630 631.
. Abdrakhmanov, I.B., Sharafutdinov, V.M., and Tolsti-
kov, G.A., Izv. Ross. Akad. Nauk, Ser. Khim., 1982,
no. 9, pp. 2160 2162.
1
20 C (3 mm Hg).
N-Tosyl-1-iodo-6-(1-methyl-2-buten-1-yl)-1,2,3,-
,4a,9a-hexahydrocarbazole XII. To a solution of
4
0
0
3
4
.41 g of amide X in 20 ml of CH Cl , we added
2
2
.85 g of NaHCO and 0.51 g of I . After the com-
3
2
plete consumption of the starting amide X ( 6 7 h),
. Abdrakhmanov, I.B., Mustafin, A.G., Tolstikov, G.A.,
et al., Zh. Org. Khim., 1986, vol. 22, pp. 613 618.
the precipitate was filtered off, and the solution was
washed with 10% aqueous Na S O (2 20 ml) and
2
2
3
5. Gataullin, R.R., Sotnikov, A.M., Abdrakhmanov, I.B.,
and Tolstikov, G.A., Mendeleev Commun., 2003, no. 5,
pp. 235 236.
water (2 10 ml) and dried over MgSO . The solvent
4
was vacuum-evaporated. Compound XII was obtained
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78 No. 3 2005