Condensation of aniline and o-hydroxyaniline with 1,2-dibromoethane

Full text of DOI:10.1023/B:RUJO.0000034957.86085.c2

Russian Journal of Organic Chemistry, Vol. 40, No. 2, 2004, pp. 284-285. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 2, 2004,
pp. 312-313.
Original Russian Text Copyright Ó 2004 by Ismailov, Mamedov, Yusubov.
SHORT
COMMUNICATIONS
Condensation of Aniline and o-Hydroxyaniline
with 1,2-Dibromoethane
V. M. Ismailov, I. A. Mamedov, and N. N. Yusubov
Baku State University, Baku, 370248 Azerbaidzhan
Received June 30, 2003
The alkylation of aniline with 3-chloro-2-chloromethyl-
1-propene is known to furnish N-(2-chloromethylpropen-
1-yl)aniline and cyclic tertiary amines [1].
to separate these compounds, and their structure and
molar ratio (7:3) were estimated from the H NMR
spectrum.
1
We demonstrated that in the presence of excess
K2CO3 in DMSO aniline I condensation with 1,2-
dibromoethane II afforded products of linear (1,2-
dianilinoethane III) and cyclic (N,N-diphenyl-1,4-diazine
IV) structure.
The composition and structure of compounds III, IV,
VI, and VII were proved by elemental analyses, IR and
1H NMR spectra
1,2-Dianilinoethane (III). To a mixture of 12.1 g
(0.13 mol) of aniline and 37.6 g (0.25 mol) of potassium
carbonate in DMSO was added dropwise 25 g (0.13 mol)
of 1,2-dibromoethane. Then the reaction mixture was
stirred for 5 h at 20°Ñ. The following 1.5 h the mixture
was stirred at 50°Ñ, then 7–8 h at 70–80°Ñ. On cooling
the mixture was treated with ethyl ether. The residue
formed on evaporating the ether was recrystallized from
2-propanol. We obtained 16 g (20%) of reaction product
III of coffee color, mp 63–65°Ñ. 1H NMR spectrum, d,
ppm: 3.25 s (4H, 2CH2), 3.75 s (2H, 2NH), 7.2 m (10H,
2C6H5). Found, %: C 88.9; H 8.7; N 14.9. C14H16N2.
Calculated, %: C 87.7; H 8.3; N 14.5.
. &2
3K1+ ꢀꢀꢀ%U&+ &+ %U
3K1+&+ &+ 1+3K
'06
,
,,
,,,
ꢁꢀ3K
1
1
3K
,9
Apparently first aniline undergoes N-alkylation with
1,2-dibromoethane in 2:1 ratio yielding reaction product
III that further enters in the condensation with another
1,2-dibromoethane molecule to form compound IV.
N,N-Diphenyl-1,4-diazine (IV). The initial mixture
prepared as above for preparation of compound III was
stirred for 1.5 h at 50°Ñ, then for 10–12 h at 110–120°Ñ.
On cooling the reaction mixture was treated with ethyl
ether. The residue formed on evaporating the ether was
recrystallized from 2-propanol. We obtained 20 g (21%)
The alkylation of o-hydroxyaniline V by dibromo-
ethane II under the same conditions occurs as N,O- and
N,N-dialkylation affording a products mixture: benzo-1,4-
oxazine VI and 2-hydroxyphenylaziridine VII. We failed
1
of reaction product IV, mp 159–160°Ñ. H NMR
ꢀ
2+ &+ &+
spectrum, d, ppm: 3.26 s (8H, 4CH2), 7.2 m (10H, 2C6H5).
Found, %: C 79.1; H 8.1; N 12.4. C16H18N2. Calculated,
%: C 80.6; H 7.6; N 11.8.
%U %U
1+
9
2+
o-Hydroxyaniline V condensation with dibromo-
ethane II. To a mixture of 100 ml of DMSO, 15 g
(0.13 mol) of o-hydroxyaniline V, and 37.6 g (0.25 mol)
of potassium carbonate was added dropwise at stirring
24.4 g (13 mol) of dibromoethane II. The reaction mixture
temperature was raised to 80°Ñ while stirring for 8 h,
. &2
'06
2
ꢀ
1
+1
9,
9,,
1070-4280/04/4002-0284Ó2004 MAIK “Nauka/Interperiodica”

285
CONDENSATION OFANILINEAND O-HYDROXYANILINE
both compounds are observed as a signal at 6.6 ppm
[8H, Ar–H in compounds VI, VII].
1H NMR spectra were recorded on spectrometer
Varian T-60, solvent CCl4, internal reference HMDS.
the mixture was treated with water and then with ethyl
ether. The extract was dried with CaCl2. On distilling
off the ether a mixture of compounds VI and VII was
1
obtained. In the H NMR spectrum of the reaction
mixture appear signals of compound VI , d, ppm: 3.9 t
REFERENCES
3
[2H, OCH2, J (HH) 7.5 Hz], 3.25 m [2H, NCH2,
3J (HH) 7.5 Hz], and compound VII: 1.9 d.d [4H, of
aziridine ring, J (HH) 2.5 Hz]. The phenyl protons of
1. Lukin, S.S., Levashova, V.I., Bunin-Krivorukova, L.I., and
Zlotskii, S.S., Zh. Org. Khim., 1989, vol. 25, p. 2453.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004