Reaction of 2,4-dibromoquinoline with hydrogen chloride

Full text of DOI:10.1023/A:1015331531268

Russian Journal of Organic Chemistry, Vol. 38, No. 1, 2002, pp. 137 138. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 1, 2002,
pp. 143 144.
Original Russian Text Copyright
2002 by Andreev, Nizhnik.
SHORT
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Reaction of 2,4-Dibromoquinoline with Hydrogen Chloride
V. P. Andreev and Ya. P. Nizhnik
Petrozavodsk State University, pr. Lenina 33, Petrozavodsk, 185640 Russia
e-mail: andreev@mainpgu.karelia.ru
Received January 10, 2001
It is known that nucleophilic aromatic substitution
in nitrogen-containing heterocycles by the action of
such weak nucleophiles as halide ions is very difficult
We have found that the same method for activation
of S Ar can be applied to substitution in the quinoline
N
ring having no N-oxide moiety. The structure of the
to occur, even when the heteroring is activated by products obtained from 2,4-dibromo-, 2-bromo-4-
N-oxide moiety. For example, replacement of nitro
chloro-, and 2,4-dichloroquinolines I III depends on
group in heteroaromatic N-oxides requires severe the conditions. The reaction of dibromoquinoline I
conditions: heating with concentrated hydrohalic acids
at the boiling boint or using acetyl or phosphinoyl
with HCl in acetonitrile gave product III as a result
of replacement of both bromine atoms by chlorine.
When gaseous hydrogen chloride was passed through
a solution of 2,4-dibromoquinoline in acetonitrile,
monosubstitution product II was formed quickly and
quantitatively. On prolonged reaction, compound II
was slowly (by 35% in 4 h) converted into dichloro
derivative III. The same reaction in chloroform gave
only 2-bromo-4-chloroquinoline (II) in quantitative
yield. No halogen replacement occurred on passing
gaseous hydrogen chloride through a solution of I in
hexane, but 2,4-dibromoquinoline hydrochloride was
quantitatively formed. Thus, by varying the solvent
polarity we can obtain in quantitative yield 2,4-di-
bromoquinoline hydrochloride and the corresponding
mono- or dichloro analogs.
halides [1]. According to the recent data, S reactions
N
of 4-nitroquinoline N-oxide in aprotic solvents are
favored by formation of molecular complexes with -
(
tetracyanoethylene) [2] and especially v-acceptors
+
(H , BF , AlCl ) [3]. As a result, the corresponding
3
3
products are formed in quantitative yield under mild
conditions.
Scheme 1.
Conditions and results of SN reactions of 2,4-dibromo-
quinoline
a
b
Tempera-
ture,
Product, yield (%),
Acid
Solvent
C
time
HCl (concd.)
65
CH CN III, 98, 30 min, or
3
IV, 98, 72 h
HCl (concd.)
HCl (gas)
HCl (gas)
20
20
20
CH CN III, 94, 20 h
CHCl3 II, 94, 60 min
3
CH CN II, 98, 5 min, or
3
III, 96, 24 h
HClO4
65
CH CN V, 81, 72 h
3
a
1
The H NMR, IR, and UV spectra and melting points of the
were consistent with published data [4].
Yield of the isolated product.
b
1
070-4280/02/3801-0137$27.00 2002 MAIK Nauka/Interperiodica

1
38
ANDREEV, NIZHNIK
Prolonged heating (for 3 days at 65 C or for 10 h
REFERENCES
at 80 C) of compound I in acetonitrile with HCl or
HBr or of compounds I III with HCl leads to almost
quantitative formation of 4-chloro-2-hydroxyquinoline
1. Ochiai, E., Aromatic Amine Oxides, Amsterdam:
Elsevier, 1967, p. 444.
(
IV) or 4-bromo-2-hydroxyquinoline (V), respectively.
Method A. A mixture of 0.5 mmol of 2,4-dibromo-
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1
994, vol. 30, no. 9, pp. 1417 1420.
quinoline and 0.2 ml of concentrated acid in 1.5 ml
of acetonitrile was kept under conditions specified
in table. When the reaction was complete (HPLC), the
mixture was evaporated to dryness, the residue was
treated with a saturated solution of sodium carbonate
to pH 8 and extracted with chloroform, the extract
was dried over anhydrous Na CO , and the solvent
3. Andreev, V.P., Kalistratova, E.G., and Ryzha-
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1
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4
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2
3
1
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was removed under reduced pressure.
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Method B. Gaseous hydrogen chloride was passed
through a solution of 0.5 mmol of 2,4-dibromoquino-
line in 1.5 ml of chloroform or acetonitrile. The mix-
ture was then treated by the procedure described
above in method A.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 1 2002