Lewis acid effects in mesitylene amination in the system NaN 3MHlgnHCl

Full text of DOI:10.1023/B:RUJO.0000043728.24619.5f

Russian Journal of Organic Chemistry, Vol. 40, No. 5, 2004, pp. 755-756. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 5, 2004,
pp. 789-790.
Original Russian Text Copyright Ó 2004 by Borodkin, Bessonov, Andreev, Shubin.
SHORT
COMMUNICATIONS
Lewis Acid Effects in Mesitylene Amination in the System
NaN3–MHlgn–HCl
I. Borodkin1,2, A.A. Bessonov1,2, R.V. Andreev1, and V.G. Shubin1
1Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Divisoion, Russian Academy of Sciences
Novosibirsk, 630090 Russia
e-mail: gibor@nioch.nsc.ru
2Novosibirsk State University Novosibirsk, 630090 Russia
Received December 9, 2003
In recent year an interest grew to direct electrophilic
amination of arenas (see [1–13] and references therein).
One among promising reagents for this reaction is so-
dium azide under conditions of acid catalysis [11–13].
These studies were applied to electrophilic amination of
benzene and its derivatives in a system NaN3–AlCl3–
HCl. The best results were obtained at the use as solvent
of the excess aromatic substrate [11] or dichloroethane
[12, 13]. Only AlCl3 served as Lewis acid [11–13].
Mesitylene conversion in amination by a system NaN3–MHlgn–
HCl, and enthalpy variation at stages (1) and (2) (DDH1 and
DDH2 respectively) calculated by PM3a procedure
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The goal of this study was an attempt to involve other
Lewis acids into this reaction and to find the media most
suitable thereto. The effect of Lewis acid in electrophilic
amination of arenas with the use of system NaN3–
MHlgn–HCl was studied by an example of mesitylene in
dichloroethane as solvent.
ꢁꢂꢇꢃꢀ“ꢀꢁꢂꢁꢃꢀꢀ ꢀꢀꢀꢀꢀꢀꢅꢈꢂꢄꢀ
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We established that mesitylene conversion strongly
depended on the Lewis acid nature.At application of acids
like TiCl4 and SnCl4 the conversion was very low, and
GeCl4 and SbCl3 were quite useless for amination (see
table). Acids SbCl5, FeCl3, and AlBr3 are moderately ac-
tive, and the most suitable for amination proved to be
GaCl3, ZrCl4, andAlCl3.
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For some Lewis acids no calculations were performed for the
parametrizations of the central atom was lacking.
b h is .the rlative molar fraction of mesidine with respect to NaN3.
Average h values are given obtained by 1H NMR spectroscopy and
GC-MS method for 2-3 runs.
The most probable reaction mechanism is presented
on the scheme (cf. [11–13]).
ñ Data from [12, 13].
d GC-MS data.
According to the scheme the nature of the Lewis acid
apparently should not notably affect the stages (3) and
(4), but its influence would have been observed in the
stages (1) and (2). In the first stage sodium azide inter-
acts with the Lewis acid (cf. [11–13]) and therefore if
that is the most exothermic. The protonation stage for
intermediate MHlgn–1N3 (A) is endothermic and it ap-
parently governs the relative reaction rates. This state-
ment is supported by the observed trend in growing mesi-
tylene conversion h with decresing DDH2 values. The
analysis based on the quantum-chemical calculations does
–
the metal cation weakly interacts with N3 anion the re-
action would be hampered. The calculations by PM3 pro-
cedure revealed that enthalpy variations for stage (1)
are very small (see table) save the reaction with AlBr3
1070-4280/04/4005-0755Ó2004 MAIK “Nauka/Interperiodica”

756
BORODKIN et al.
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(2)
and HMDS (dH 0.04 ppm.). GC-MS measurements were
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carried out on Hewlett Packard G1800A instrument in-
cluding a gas chromatograph HP5890 and a mass-selec-
tive detector HP5971. Ionizing electrons energy 70 eV,
oven heating mode as follows: 2 min at 50°C, then heat-
ing at a rate 10 deg/min till 280°C, column 30000´0.25
mm, stationary phase copolymer HP-5MB (5% of diphe-
nyl-, 95% dimethulsiloxane), carrier gas helium, flow rate
1 ml/min. The quantitative analysis of mixtures was per-
formed by internal normalization
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The study was carried out under financial support of
the Russian Foundation for Basic Research (grant no.
02-03-32431).
1+
REFERNCES
+
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not take into account the solvent effects and the state of
aggregation of the reactants and thus should be regarded
as preliminary.
The activity series for Lewis acid we obtained (GaCl3
~ ZrCl4 ~ AlCl3 >AlBr3 > FeCl3 > SbCl5 >> SnCl4, TiCl4
> SbCl3, GeCl4) is unlike that observed for catalysts of
Friedel-Crafts reaction (Al2Br6 > Al2Cl6 > Ga2Cl6 >
Fe2Cl6 > SbCl5 > ZrCl4, SnCl4 > SbCl3) [14] (cf. [15]). A
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whereas in arene amination with the system NaN3–
MHlgn–HCl they are fairly inert.
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The results obtained are consitent with existing obser-
vations that the activity of Lewis acids cannot be ex-
pressed by a unique series.
General procedure for mesitylene amination. A
dispersion of dry NaN3 (3.65 mmol) and anhydrous Lewis
acid (3.65 mmol) in 4 mi of anhydrous ClCH2CH2Cl was
stirred for 20 h at room temperature. On adding mesity-
lene (7.3 mmol) into the reaction mixture was passed at
stirring for 2 h dry hydrogen chloride at 20–25°C. Then
the mixture was poured on ice, treated with excess concn.
NaOH solution, extracted with Et2O (3´15ml), dried on
MgSO4, and ether was distilled off. The products compo-
sition was analysed by 1H NMR and GC–MS methods.
NMR spectra of solutions in CDCl3 were registered
on spectrometers Bruker AC-200 and WP-200-SY, in-
ternal references residual protons in CDCl3 (dH 7.24 ppm)
16. Kobayashi, S., Busujima, T., and Nagayama, S., Chem. Eur.
J., 2000, vol. 6, p. 3491.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 5 2004