Vicarious c-amination of nitrobenzene

Full text of DOI:10.1023/A:1012482103171

Russian Journal of Organic Chemistry, Vol. 37, No. 6, 2001, pp. 887 888. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 6, 2001,
pp. 933 934.
Original Russian Text Copyright 2001 by Krylova, Elokhina, Nakhmanovich, Larina, Lopyrev.
SHORT
COMMUNICATIONS
*
Vicarious C-Amination of Nitrobenzene
O. V. Krylova, V. N. Elokhina, A. S. Nakhmanovich, L. I. Larina, and V. A. Lopyrev
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
Received July 4, 2000
Vicarious nucleophilic substitution of hydrogen is
a convenient method of nucleophiles introduction into
aromatic [1 3] and heterocyclic [4 7] rings.
It is known that in reactions of vicarious C-amina-
tion of nitrobenzene and its derivatives 1,1,1-tri-
methylhydrazinium iodide is used as aminating agent
in the presence of t-BuOK or MeONa. As a result
arises a mixture of o- and p-nitroanilines in 2: 1
ratio [8]. In [9] vicarious amination of nitrobenzene
was carried out with sulfenamides in DMF in the
(1)
presence of t-BuOK to obtain also a mixture of o-
and p-nitroanilines in an overall yield 69 85%.
We established that the reaction of 1,1,1-tri-
methylhydrazinium bromide (I), chloride (II), and
iodide (III) in anhydrous DMSO in the presence
of t-BuOK at 20 C yielded not only p-nitroaniline
(V) but also bis(p-nitrophenyl)amine (VII)
at any halogen anion in the reagent.
To reveal the formation path of amine VII in
the course of the process we attempted to carry out a
reaction of p-nitroaniline with iodide III in
anhydrous DMSO in the presence of t-BuOK. How-
ever from the reaction mixture only the original
p-nitroaniline was recovered. In reaction of equimolar
quantities of nitrobenzene, p-nitroaniline (V), and
iodide III under the same conditions we obtained
bis(p-nitrophenyl)amine (VII) in 60% yield.
(2)
X = Br (I), Cl (II), I (III).
Apparently the vicarious C-amination of nitro-
benzene includes two parallel reactions.
tion arises an amino-anion VI that reacts with
nitrobenzene to furnish compound VII; here is felt
the ammonia odor. p-Nitroaniline (V) and
bis(p-nitrophenyl)amine (VII) were isolated from the
reaction mixture by fractional crystallization.
The first stage of nitrobenzene reaction with
halides I III apparently proceeds via intermediate
formation of carbanion IV resulting from leaving
of anion X and through proton elimination from the
para-position in the nitrobenzene molecule as HX
induced by the base. In the second stage of the reac-
Nitrobenzene reaction with 1,1,1-trimethylhydr-
azinium bromide (I). To a solution of 2.4 g
(
0.02 mol) of nitrobenzene in 40 ml of anhydrous
*
The study was carried out under financial support of the
DMSO was added slowly at stirring 3.88 g
(0.025 mol) of bromide I. The mixture was stirred till
complete dissolution, and thereto was added 5.6 g
Russian
Foundation
for
Basic
Research
(grant
no. 98-03-32899).
1
070-4280/01/3706-0887$25.00 2001 MAIK Nauka/Interperiodica

888
KRYLOVA et al.
(
0.05 mol) of dry t-BuOK. Immediately the reaction
similar way for 4 h. From 2.46 g (0.02 mol) of nitro-
benzene and 5.05 g (0.025 mol) of iodide III we
obtained 0.5 g (18%) of compound V and 0.6 g
(13%) of compound VII. In reaction carried out for
10 h the yields of compounds V and VII were
8 and 19% respectively. In 40 h was obtained only
compound VII in 47% yield.
mixture became bright red. The mixture was stirred
at 20 C for 4 h, then poured on ice, acidified to pH 3
with 10% hydrochloric acid. The mixture was cooled
to 0 C, the separated precipitate was filtered off, the
filtrate was extracted with ethyl acetate (3 20 ml),
the extract was washed with 40 ml of water and dried
with MgSO . The ethyl acetate was evaporated in a
4
Nitrobenzene reaction with p-nitroaniline and
vacuum to dryness, and the residue was combined
with the previously obtained precipitate. The
combined solids were dissolved in MeOH, filtered,
the filtrate was cooled to 0 C, and the precipitated
p-nitroaniline (V) was filtered off. Yield of nitro-
amine V 0.55 g (20%), mp 147 C (mp 146
1
,1,1-trimethylhydrazinium iodide (III) was
carried out in a similar way for 10 h. From 2.46 g
0.02 mol) of nitrobenzene, 2.76 g (0.02 mol) of
(
p-nitroaniline, and 5.05 g (0.025 mol) of iodide III
we obtained 3.1 g (60%) of compound VII.
1
47 C [10]). The residue insoluble in methanol was
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(
VII) 0.7 g (14%), mp 216 217 C (mp 216 C [11]).
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5
6
7
8
9
1
Compound VII. IR spectrum ( , cm ): 1320,
1
1
9
580, 3300. H NMR spectrum (DMSO-d , , ppm):
6
3
.92 s (1H, NH), 7.35 8.20 m (8H, JHH 9.5
1
5
Hz). N NMR spectrum (DMSO-d6, N, ppm):
71.84 (NH), 10.7 (NO2). Found, %:
5.48; 3.52; 16.30. C H N O .
Calculated, %: C 55.60; H 3.47; N 16.22.
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C
5
H
N
1
2
9
3
4
Nitrobenzene reaction with 1,1,1-trimethylhydr-
azinium chloride (II) was carried out in a similar
way for 4 h. From 2.46 g (0.02 mol) of nitrobenzene
and 2.76 g (0.025 mol) of chloride II we obtained
0
.8 g (29%) of compound V and 0.4 g (8%) of
compound VII.
1
992, vol. 57, pp. 4784 4785.
Nitrobenzene reaction with 1,1,1-trimethyl-
hydrazinium iodide (III) was carried out in a
10. Beilst. H, vol. 12, p. 711.
11. Beilst. H, vol. 12, p. 716.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001