1574
ZARAISKII, KACHURIN
subjected to fractional distillation on Vigreux column
30 40 cm long. After distilling off the acetic acid and
the traces of unreacted acetic anhydride the main
fraction was collected at 54 57 C (20 mm Hg). The
yield almost quantitative. n2D0 1.4547 (1.4540 [19],
The residual acenaphthene was removed by sublima-
tion in a vacuum (1 mm Hg) at 80 100 C, and at the
bath temperature 185 C was distilled off 0.18 g of
reaction product IVb of 97% purity which crystalliz-
ed at cooling. After 2-fold recrystallization from
1
1
methanol mp 49.1 C. H NMR spectrum (CD2CI2,
1.4570 [20]). H NMR spectrum (CD3CN, TMS), ,
TMS), , ppm: 2.01 s (3H, CH3), 4.07 s (2H, SCH2),
3.38 s (4H, CH2CH2), 7.30 d (2 1H), 7.20 d (1H),
7.48t (1H), 7.77d (1H). Found, %: C 77.86; H 6.54;
S 15.25. C14H14S. Calculated, %: C 78.46; H 6.58;
S 14.96.
ppm: 2.03 s (3H, SCH3), 2.20 s (3H, CCH3), 5.10 s
(2H, SCH2O). Found, %: C 40.46; H 6.88; S 25.95.
C4H8O2S. Calculated, %: C 39.98; H 6.71; S 26.68.
Methylthiomethylation under conditions of
phasetransfer catalysis. Into a flask with a conical
pointed bottom equipped with a thermometer and
an agitator with short blades was charged 10 mmol
of substrate II, 10 mmol of reagent III, internal
reference (n-alkane), and phase-transfer agent for
electrophile, sodium tetrakis(perfluorophenyl)borate
Di(methylthiomethyl)acenaphthenes. After distil-
ling off monosubstituted compound IVb as described
above the still residue from runs nos. 5, 6 was dis-
solved in CCl4, and the solution was subjected to
chromatography on silica gel (eluent CCl4, GLC
monitoring). The fraction containing no less than
98% of disubstituted acenaphthene was collected; on
removal of solvent formed a wax-like substance, mp
50 65 C (0.10 g). Found, %: C 69.73; H 6.66;
S 23.43. C16H18S2. Calculated, %: C 70.02; H 6.61;
S 23.37.
or N,N-dimethyl-N-octadecyltaurobetaine [17] (1.5
1*
3 mmol l
in solvent IIc). The total volume of
organic phase was 10 ml.
The reaction was initiated by adding 5 ml of heated
sulfuric acid solution. Intermittently sampling of
organic phase was performed, the samples of 0.15 ml
were washed with saturated water solution of sodium
hydrogen carbonate and analyzed by GLC.
(Methylthiomethyl)toluene (IVc) was isolated
from the final reaction mixture (see table, run no. 7)
by procedure described above for compound IVa. We
obtained 0.148 g of product containing 5% of un-
(Methylthiomethyl)anisoles (IVa) (isomers mix-
ture). From the final reaction mixture (see table, run
no. 1) after distilling off the solvent and unreacted
substrate was collected 0.435 g of colorless distillate
at 1 mm Hg and bath temperature 100 C. According
to GLC the distillate contained two components in
7: 1 ratio and about 2% of substituted toluene (IVc)
admixture. Found, %: C 65.23; H 7.29; S 18.76.
C9H12OS. Calculated , %: C 64.24; H 7.12; S 19.05.
n2D0 1.5670 (1.5660 [14] for 4-substituted anisole).
1
identified impurities. The H NMR spectrum cor-
responded to the 4-substituted IVc with an admixture
likely to be composed of isomeric products. Found,
%: C 72.29; H 7.77; S 19.72. C9H12S. Calculated,
%: C 71.02; H 7.95; S 21.03. n2D0 1.5495 (1.5599
[5] for 2-substituted isomer).
REFERENCES
1. Kantor, S.W., Hauser, C.R., J. Am. Chem. Soc.,
1951, vol. 73, p. 4122; Burdon, M.G. and Mof-
fatt, J.G., J. Am. Chem. Soc, 1966, vol. 88, p. 5855;
Pettit, G.R. and Brown, T.H., Canad. J. Chem, 1967,
vol. 45, p. 1306; Claus, P., Monatsh. Chem, 1968,
vol. 99, p. 1034; Claus, P. and Vyculidic, W.,
Tetrahedron Lett., 1968, p. 3607; Claus, P., Monatsh.
Chem., 1971, vol. 102, p. 913; Claus, P. and
Vyculidic, W., Monatsh. Chem., 1971, vol. 102,
p. 1571; Marino, J.P., Pfitzner, K.E., and Olof-
son, R.A., Tetrahedron, 1971, vol. 27, p. 4181;
Claus, P. and Rieder, W., Monatsh. Chem., 1972,
vol. 103, p. 163; Gassman, P.G. and Gruetzmacher, G.,
J. Am. Chem. Soc., 1973, vol. 95, p. 588; Gass-
man, P.G. and Amick, D.R., J. Am. Chem. Soc., 1978,
vol. 100, p. 7611; Sato, K., Iwone, S., and Ozawa, K.,
J. Chem. Soc., Perkin Trans. I, 1984, p. 2715.
2. Poppelsdorf, F. Holt, S.J., J. Chem. Soc., 1954,
5-(Methylthiomethyl)acenaphthene(IVb). A mix-
ture of arene IIb (1.64 g, 10 mmol) and ester III
(1.10 ml, 10 mmol) was heated at 55 C till the
majority of crystals were dissolved, then at shaking
was added dropwise conc. H2SO4 (0.2ml, 3.6 mmol).
The homogeneous mixture self-heated to 85 C, and it
was maintained for another 15 min. The reaction
mixture was quenched with water (5 ml), and the
emulsion formed was twice extracted with 5 ml of
benzene. The extract was washed with 20% solution
of KOH, with water, and benzene was evaporated.
The residue was treated with boiling hexane (6 2ml),
and the combined hexane solution was evaporated.
*
No phase-transfer catalysis was observed likely because of
high lipophily of cation I.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 11 2003