Regiochemistry of the reaction of deoxygenation of 1-tosylisatin with hexaethyltriamidophosphite

Full text of DOI:10.1134/S1070363211050240

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 5, pp. 964–965. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.V. Bogdanov, L.I. Musin, V.F. Mironov, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 5, pp. 877–878.
LETTERS
TO THE EDITOR
Regiochemistry of the Reaction of Deoxygenation
of 1-Tosylisatin with Hexaethyltriamidophosphite
A. V. Bogdanov, L. I. Musin, and V. F. Mironov
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
e-mail: bogdanov@iopc.ru
Received November 11, 2010
DOI: 10.1134/S1070363211050240
Deoxygenation and desulfonation of organic com-
pounds by the action of trivalent phosphorus deri-
vatives are widely used in organic chemistry [1, 2].
Among the various transformations occurring in this
case a group of processes can be separated that are
realized in the reactions of carbonyl compounds with P(III)
derivatives. For example, the reaction of trialkyl-
phosphites or sodium diethylphosphite with various
benzaldehyde derivatives gives rise to the corres-
ponding ethylenes including stilbenes [3, 4] in
moderate yields. 2,2'-Diformylbiphenyl and its deriva-
tives undergo the intramolecular cyclization to the
corresponding 1,2-diphenyloxiranes under the action
of tris(dimethylamino)phosphine [5]. It is assumed that
the deoxygenation of 1,3-dicarbonyl compounds (the
cyclic anhydrides or thioanhydrides) proceeds through
the stage of the carbene formation [6, 7]. In the re-
actions of aroyl- and hetaroylphosphonates with
trialkylphosphites the formed intermediate of carbene
nature is added intramolecularly to the multiple bond
[8–14]. Nevertheless, in a considerable number of the
studies the intermediate formation of carbenes is only
postulated, and other versions of explanation of these
synthetic results may be offered. Unlike the deoxy-
genation of ketones and carboxylic acid anhydrides,
similar processes with α-dicarbonyl compounds are
described in only few works [4, 15, 16].
In this study the reaction of tris(diethyltriamino)-
phosphine I with 1-tosylizatin II containing two
reaction center (C=O and S=O) capable of reacting
with an atom P(III) was first investigated. The
deoxygenation reaction can proceeds by two routes: at
the S=O bond to form 1-sulfinylisatin III (a) and at the
carbonyl group to give 1,1'-ditosylisoindigo IV (b).
1
3
Based on the IR and C NMR data, we un-
ambiguously established the regiochemistry of
deoxygenation reaction: The process occurs exclu-
3
sively with the participation of the oxygen of C =O
moiety (b).
SO C H Me
2
6
4
N
b
O
O
O
4
7
3
a
3
b
5
6
a
O
O
+ P(NEt2)3
O
−
OP(NEt2)3
1
2
−V
N
N
I
7a
N
V
O
S
O
S
O
O
S
8
O
a
C H Me
C H Me
6
4
6
4
9
1
0
1
2
1
III
II
1
IV
9
64

REGIOCHEMISTRY OF THE REACTION OF DEOXYGENATION
965
1
,1'-Bis(4-methylphenylsulfonyl)-1Н,1'Н-[3,3']-
Materials Science of the Russian Academy of Sciences
and by the President of the Russian Federation (grants
MK-1670.2010.3).
biindolylidene-2,2'-dione (IV). To a pale yellow
suspension of 0.5 g (1.66 mmol) of 1-tosylisatin I in
1
0
–
0 ml of methylene chloride was added dropwise
.44 ml (1.66 mmol) of hexaethyltriamidophosphite at
60°С while bubbling argon. A sharp change occurred
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6. Islam, M.R., Khayer, Kh., Akhter, A., and Duddeck, H.,
This work was financially supported by the Prog-
ramme no. 1 of the Department of Chemistry and
J. Bangladesh Chem. Soc., 2005, vol. 18, no. 1, p. 1.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 5 2011