Russian Journal of General Chemistry, Vol. 71, No. 1, 2001, p. 150. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 1, 2001,
pp. 164 165.
Original Russian Text Copyright
2001 by Kuznetsov, Brusilovskii, Mazepa, Krasnoshchekaya.
LETTERS
TO THE EDITOR
Reaction of 5,6-Benzo-1,3,2-dioxathiepane 2-Oxide
with Acetonitrile
V. V. Kuznetsov, Yu. E. Brusilovskii, A. V. Mazepa, and S. P. Krasnoshchekaya
Bogatskii Physicochemical Institute, Ukrainian National Academy of Sciences, Odessa, Ukraine
Received April 13, 2000
It is known that the reaction of some six-membered
1,3- and 1,3,2-heterocycles, e.g., 4,4,6-trimethyl-1,3,2-
dioxathiane 2-oxide, with acetonitrile yields 2-methyl-
5,6-dihydro-4H-1,3-oxazines [1,2]. Here we report on
the previously unknown similar reaction of seven-
membered cyclic sulfites, with the transformation of
5,6-benzo-1,3,2-dioxathiepane 2-oxide I into 5,6-ben-
zo-2-methyl-4,7-dihydro-1,3-oxazepine II as exam-
ple. Hydrolysis of the latter gives 1-hydroxymethyl-
2-aminomethylbenzene III.
The discovered reaction broadens the spectrum of
chemical transformations of seven-membered cyclic
sulfites and is a new route to benz-1,3-oxazepines and
the corresponding 1,4-amino alcohols.
The initial sulfite I was prepared according to [3] in
a 92% yield. Its physicochemical and 1H NMR param-
eters were in agreement with the published data [3 5].
To a solution of 0.037 mol of I in 42 ml of aceto-
nitrile, 15 ml of concentrated sulfuric acid was slowly
added dropwise with stirring. After that the reaction
mixture was refluxed on a water bath for 3 h. Excess
acetonitrile was removed on a rotary evaporator, and
the viscous residue was diluted with 100 ml of water
and extracted with chloroform (2 50 ml). The re-
maining aqueous phase was treated with solid lithium
hydroxide to pH 9 10, at cooling with ice. The pre-
cipitate of II (3.8 g) was filtered off, and the aqueous
phase was extracted with chloroform (4 50 ml).
After removing the solvent, 1.4 g of amino alcohol
III was isolated.
1) H2SO4, CH3CN;
O
O
O
2) LiOH
S O
C CH3
N
II
I
OH
OH
NH2
III
Oxazepine II is a colorless crystalline substance
decomposing at 185 C. It was obtained in a 64% yield.
Its composition and structure were confirmed by IR
The IR spectra were recorded on a Specord IR-75
spectrophotometer in thin layer, in Vaseline oil, and
in CHCl3 solutions (layer thickness 0.112 mm).
The 1H NMR spectra were measured on a Tesla
BS 497 spectrometer for 15% solutions in CDCl3 re-
lative to internal TMS. The mass spectrum was ob-
tained on an MKh-1321 spectrometer with the ioniz-
ing electron energy of 70 eV.
1
and H NMR spectroscopy and by mass spectrometry.
1
The H NMR spectrum contains the expected signals
of all groups of protons, , ppm: 1.91 s (3H), 4.10 s
(2H), 4.42 s (2H), 7.19 s (4H). The IR spectrum con-
tains intense absorption bands at 1655 (C=N) and
1
1510 cm (C=Carom ). The mass spectrum contains
a peak of molecular ion (m/z 161) and the base peak
with m/z 119 corresponding to the fragmentation:
REFERENCES
+
O
1. Kuznetsov, V.V., Khim. Geterotsikl. Soedin., 1996,
C CH3
O+
no. 2, p. 275.
CH3CNH
N
2. Kuznetsov, V.V., Abstracts of Papers, XVII Ukrains’ka
konferentsiya z organichnoi khimii (XVII Ukrainian
Conf. on Organic Chemistry), Kharkov, 1995, p. 191.
3. Riemschneider R. and Wuscherpfennig V., Z. Natur-
forsch. (b), 1962, vol. 17, no. 8, pp. 516 522.
4. Faucher, H., Guimaraes, A.S., and Robert, J.B., Tetra-
hedron Lett., 1977, no. 20, pp. 1743 1746.
5. Faucher, H., Guimaraes, A.C., Robert, J.B., Sau-
riol, F., and St.-Jacques, M., Tetrahedron, 1981,
vol. 37, no. 4, pp. 689 701.
m/z 161 (Irel 70%)
m/z 119 (Irel 100%)
Along with compound II, amino alcohol III was
isolated (yield 28% based on the starting sulfite) as
a viscous liquid with the characteristic amine odor.
1H NMR spectrum, , ppm: 3.53 s (3H), 3.75 s (2H),
4.48 s (2H), 7.14 s (4H). The IR spectrum contains
1
absorption bands at 3430 3290 cm (OH, NH), and
1
also at 1580 and 1510 cm (C=Carom ).
1070-3632/01/7101-0150$25.00 2001 MAIK Nauka/Interperiodica
Kuznetsov
