Reactions of N,N′-Bis(methoxycarbonyl)-p-benzoquinonediimine with β-Tosyl carbonyl compounds

Full text of DOI:10.1023/A:1012407423432

Russian Journal of Organic Chemistry, Vol. 37, No. 7, 2001, pp. 1054 1055. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 7, 2001,
pp. 1100 1101.
Original Russian Text Copyright
2001 by Velikorodov, Mochalin.
SHORT
COMMUNICATIONS
Reactions of N,N -Bis(methoxycarbonyl)-p-benzoquinonediimine
with -Tosyl Carbonyl Compounds
A. V. Velikorodov and V. B. Mochalin
Astrakhan State Pedagogical University, ul. Tatishcheva 20a, Astrakhan, 414056 Russia
e-mail: astpedun@astranet.ru
Received December 27, 2000
Reactions of mono- and disulfonyl derivatives of
benzoquinonimines with various -dicarbonyl com-
pounds have been well documented [1]. We reported
in [2] on the synthesis of carbamate indole derivatives
from the corresponding Michael adducts of N,N -bis-
(methoxycarbonyl)-p-benzoquinonediimine (I) and
-diketones or -keto esters. There are almost no
published data on reactions of -sulfonyl carbonyl
compounds with quinoid structures [3, 4]. On the
other hand, -sulfonyl ketones are fairly strong CH
acids (pK 10) [5]. With the goal of obtaining new
polyfunctional carbamate derivatives of indole
(which attract interest from the viewpoint of biological
activity), in the present work we examined reactions
of compound I with tosylacetone (IIa), tosylaceto-
phenone (IIb), and ethyl tosylacetate (IIc) in dioxane
at 20 C in the presence of sodium methoxide.
Unlike initial quinonediimine I, compounds III
showed in the IR spectra absorption bands at 3330
1
3335 cm due to stretching vibrations of the NH
1
group, 1600 1515 cm (C Carom), and 1140 1145
1
and 1310 1315 cm (antisymmetric and symmetric
vibrations of the sulfonyl group).
We failed to obtain the corresponding Michael
adduct from quinonediimine I and ethyl tosylacetate
(IIc) in dioxane or benzene in the presence of MeONa
or Et3N. In all cases, strong tarring occurred. By
heating adducts IIIa and IIIb in 22% hydrochloric
acid for 1.5 h [2] we synthesized indole derivatives
IVa and IVb whose structure was confirmed by the
1H NMR spectra.
According to the data of elemental analysis and
IR spectroscopy, the products were the corresponding
Michael adducts IIIa and IIIb:
IV, R = Me (a), Ph (b).
We also examined the possibility for synthesizing
indoles IVa and IVb in one step, following the proce-
dure reported in [2]. As with -diketones, the reaction
of I with -tosyl ketones IIa and IIb stopped at the
stage of formation of the corresponding 1,4-bis-
(methoxycarbonylamino)benzenes IIIa and IIIb in 69
and 71% yield, repsectively.
Tosyl derivatives IIa IIc were prepared by heating
in ethanol for 6 h at 70 C equimolar amounts of
sodium p-toluenesulfinate dihydrate [6] and chloro-
acetone [7], phenacyl bromide, or ethyl chloroacetate
[6], respectively. Tosylacetone (IIa): yield 55%,
mp 52 C (published data [8]: mp 52 54 C); tosyl-
II, III, R = Me (a), Ph (b).
1070-4280/01/3707-1054$25.00 2001 MAIK Nauka/Interperiodica

REACTIONS OF N,N -BIS(METHOXYCARBONYL)-p-BENZOQUINONEDIIMINE
1055
acetophenone (IIb): yield 72%, mp 110 C (published
data [8]: mp 109 110 C); ethyl tosylacetate (IIc):
yield 63%, mp 34 C (from diethyl ether). Found, %:
C 54.32; H 6.01; S 13.11. C11H14O4S. Calculated, %:
C 54.55; H 5.79; S 13.22.
1,4-Bis(methoxycarbonylamino)-2-(2-oxo-1-tosyl-
propyl)benzene (IIIa). To a solution of 4.5 mmol of
quinonediimine I in 10 ml of anhydrous dioxane
we added 4.6 mmol of ketone IIa and 0.04 g of
sodium methoxide, the mixture was kept for 8 h at
20 C, 2 3 drops of glacial acetic acid was added,
and the mixture was poured into 100 ml of water.
The precipitate was filtered off, dried in air, and
recrystallized from ethanol. Yield 72%, mp 148 C.
Found, %: C 54.85; H 5.34; N 6.66. C20H22N2O7S.
Calculated, %: C 55.30; H 5.07; N 6.45.
described above for compound IVa. Yield 79%,
mp 172 C. H NMR spectrum, , ppm: 8.75 br.s
1
(1H, NH), 8.49 s (1H, 4-H), 8.07 d (1H, Harom, J =
11 Hz), 7.70 d (1H, Harom, J = 11 Hz), 7.55 7.38 m
(5H, Harom), 7.32 d (2H, Harom, J = 10 Hz), 7.22 d
(2H, Harom, J = 10 Hz), 3.78 s (3H, OMe), 3.68 s
(3H, OMe), 2.70 s (3H, Me). Found, %: C 63.07;
H 4.41; N 5.80. C25H22N2O6S. Calculated, %:
C 62.76; H 4.60; N 5.68.
1
The H NMR spectra were taken on a Bruker AM-
300 spectrometer (300 MHz) in acetone-d6 using TMS
as internal reference. The IR spectra were recorded on
1
an IKS-29 spectrophotometer (4000 400 cm ) in
mineral oil.
REFERENCES
1,4-Bis(methoxycarbonylamino)-2-(2-oxo-2-
phenyl-1-tosylethyl)benzene (IIIb) was synthesized
in a similar way. Yield 89%, mp 132 C. Found, %:
C 60.67; H 4.51; N 5.72. C25H24N2O7S. Calculated,
%: C 60.48; H 4.84; N 5.65.
1. Adams, R. and Reifschneider, W., Bull. Soc. Chim.
Fr., 1958, no. 1, pp. 23 65.
2. Velikorodov, A.V. and Mochalin, V.B., Russ. J. Org.
Chem., 1998, vol. 34, no. 10, pp. 1490 1493.
3. Fujita, S., J. Synth. Org. Chem. Jpn., 1985, vol. 43,
Methyl 5-methoxycarbonylamino-3-tosylindole-
1-carboxylate (IVa). A suspension of 2.3 mmol of
adduct IIIa in 20 ml of 22% hydrochloric acid was
refluxed for 1.5 h. It was then cooled, and the precip-
itate was filtered off, dried in air, and recrystallized
no. 2, pp. 153 166.
4. Velikorodov, A.V., Sarmin, I.A., and Semenova, E.B.,
Izv. Vyssh. Uchebn. Zaved., Ser. Khim. Khim. Tekh-
nol., 1999, vol. 42, no. 2, pp. 13 19.
1
5. Technique of Organic Chemistry, Weissberger, A.,
from glacial acetic acid. Yield 76%, mp 163 C. H
Ed., New York: Intersci., 1962, 3rd ed., vol. 2.
NMR spectrum, , ppm: 8.72 br.s (1H, NH), 8.49 s
(1H, 4-H), 7.98 d (1H, Harom, J = 11 Hz), 7.65 d
(1H, Harom, J = 11 Hz), 7.34 d (2H, Harom, J = 10 Hz),
7.22 d (2H, Harom, J = 10 Hz), 3.79 s (3H, OMe),
3.68 s (3H, OMe), 2.80 s (3H, Me), 2.72 s (3H, Me).
Found, %: C 57.52; H 5.06; N 7.08. C20H20N2O6S.
Calculated, %: C 57.69; H 4.81; N 6.73.
6. Tietze, L.-F. and Eicher, T., Reactions and Syntheses
in the Organic Chemistry Laboratory, Mill Valley,
California: University Science Books, 1989.
7. Weygand Hilgetag Organisch-chemische Experi-
mentierkunst, Hilgetag, G. and Martini, A., Eds.,
Leipzig: Johann Ambrosius Barth, 1964, 3rd ed.
Methyl 5-methoxycarbonylamino-2-phenyl-3-
tosylindole-1-carboxylate (IVb) was synthesized as
8. Vennstra, G.E. and Zwanenburg, B., Synthesis, 1975,
no. 6, pp. 519 529.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 7 2001