Applications of Baylis-Hillman chemistry: One-pot convenient synthesis of functionalized (1H)-quinol-2-ones and quinolines

Article abstract of DOI:10.1016/S0040-4020(02)00332-0

A simple synthesis of functionalized (1H)-quinol-2-ones and quinolines from the Baylis-Hillman adducts, i.e. alkyl 3-hydroxy-2-methylene-3-arylpropanoates and β-hydroxy-α-methylene-β-arylalkanones, respectively, has been described.

Full text of DOI:10.1016/S0040-4020(02)00332-0

TETRAHEDRON
Pergamon
Tetrahedron 58 )2002ꢀ 3693±3697
Applications of Baylis±Hillman chemistry: one-pot convenient
synthesis of functionalized ꢀ1H)-quinol-2-ones and quinolines
p
Deevi Basavaiah, Ravi Mallikarjuna Reddy, Nagaswamy Kumaragurubaran
and Duddu S. Sharada
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India
Received 29 November 2001; accepted 22 March 2002
AbstractÐA simple synthesis of functionalized )1Hꢀ-quinol-2-ones and quinolines from the Baylis±Hillman adducts, i.e. alkyl 3-hydroxy-
2-methylene-3-arylpropanoates and b-hydroxy-a-methylene-b-arylalkanones, respectively, has been described. q 2002 Elsevier Science
Ltd. All rights reserved.
The )1Hꢀ-quinol-2-one moiety, often referred to as a carbo-
styril moiety, is an important structural unit present in many
chemistry, we required 3-acetoxymethyl-)1Hꢀ-quinol-2-
one and their derivatives. Recently Kaye and co-workers
have reported an interesting transformation of the Baylis±
Hillman adducts derived from 2-nitrobenzaldehyde, into
quinoline derivatives via catalytic hydrogenation using
1
±5
biologically active molecules. Also the quinoline frame-
work constitutes an integral part of several natural products,
many of which possess interesting physiological proper-
6
,7
24
ties. Due to their interesting and important biological
properties a number of methods are reported in the literature
for the synthesis of )1Hꢀ-quinol-2-one and quinoline deriva-
tives with different substitution pro®les and in fact, develop-
ment of new and ef®cient methods for the preparation of
these important molecules still continues to be an interesting
and attractive area of research in synthetic organic
Pd/C. More recently Kim and co-workers have described
an attractive synthesis of 3-ethoxycarbonyl-4-hydroxy-
quinoline N-oxides via the treatment of Baylis±Hillman
adducts of various 2-nitrobenzaldehydes with tri¯uoroacetic
2
5
acid. Subsequently Kim has also reported a general
synthesis of 3-quinolinecarboxylic acid esters from the
Baylis±Hillman adducts derived from o-halobenzaldehyde
8
±13
26
chemistry.
molecules,
In continuation of our interest in heterocyclic
we herein report a simple and facile one-pot
synthesis of functionalized )1Hꢀ-quinol-2-one and quinoline
N-tosylimines.
1
4,15
It occurred to us that it would be useful if we could directly
convert acetates of Baylis±Hillman adducts, derived from
derivatives using Baylis±Hillman adducts.
2-nitrobenzaldehydes, into the required 3-acetoxymethyl-
In recent years, the Baylis±Hillman carbon±carbon bond
forming reaction has become increasingly important
because it is an atom economical reaction and provides an
unique class of attractive densely functionalized molecules,
whose applications in a multitude of synthetic organic trans-
)1Hꢀ-quinol-2-one and their derivatives by treatment with
an appropriate reagent, if possible in a one-pot operation. In
this direction we ®rst examined application of Fe/acetic
acid for the transformation of methyl 3-acetoxy-3-)2-
nitrophenylꢀ-2-methylenepropanoate )2aꢀ, obtained from
methyl 3-hydroxy-3-)2-nitrophenylꢀ-2-methylenepropano-
ate )1aꢀ via the treatment with acetyl chloride/pyridine,
2
7
1
6±23
formations have been well documented in the literature.
During our on-going research program on heterocyclic
Scheme 1.
Keywords: Baylis±Hillman chemistry; Fe/acetic acid; )1Hꢀ-quinol-2-ones and quinolines.
Corresponding author. Tel.: 191-40-3010221; fax: 191-40-3012460; e-mail: dbsc@uohyd.ernet.in
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020)02ꢀ00 332-0

3694
D.Basavaiah et al./ Tetrahedron 58 %2002) 3693±3697
Scheme 2.
into the required 3-acetoxymethyl-)1Hꢀ-quinol-2-one )3ꢀ.
Interestingly, we found that treatment of methyl 3-acetoxy-
acid at 1108C for 30min, after usual work-up and crystal-
lization from chloroform and hexanes )1:1ꢀ. This is a very
encouraging result in the sense that the reaction directly
provides the desired 3-acetoxymethyl-)1Hꢀ-quinol-2-one,
as acetic acid also acts as a source for the acetoxy group.
We then successfully transformed a representative class of
Baylis±Hillman adducts )1b±dꢀ, derived from the corre-
sponding ortho-nitrobenzaldehydes and alkyl acrylates,
into 3-acetoxymethyl-)1Hꢀ-quinol-2-one derivatives )3±5ꢀ
)Scheme 2, Table 1ꢀ.
3
-)2-nitrophenylꢀ-2-methylenepropanoate )2aꢀ with Fe/
acetic acid at 1108C for 30min provided 3-acetoxy-
methyl-)1Hꢀ-quinol-2-one )3ꢀ in 71% isolated yield
)
Scheme 1ꢀ.
At this stage we envisioned that the treatment of methyl
-hydroxy-3-)2-nitrophenylꢀ-2-methylenepropanoate )1aꢀ
directly with Fe/acetic acid might provide the desired
-acetoxymethyl-)1Hꢀ-quinol-2-one )3ꢀ due to the presence
3
3
of acetic acid, which might provide the desired acetoxy
substitution. We have indeed obtained the desired product
3 in 77% yield when we treated methyl 3-hydroxy-3-)2-
nitrophenylꢀ-2-methylenepropanoate )1aꢀ with Fe/acetic
With a view to understanding the generality of this reaction,
we have extended the same strategy to 4-hydroxy-4-)2-
nitrophenylꢀ-3-methylenebutan-2-one )1eꢀ, the Baylis±
Hillman adduct derived from 2-nitrobenzaldehyde and
methyl vinyl ketone. Thus, the treatment of 4-hydroxy-4-
)2-nitrophenylꢀ-3-methylenebutan-2-one )1eꢀ, with Fe/acetic
acid at 1108C for 30min provided the desired 3-acetoxy-
methyl-2-methylquinoline )6ꢀ in 63% isolated yield after
usual work-up followed by column chromatography
and crystallization from chloroform and hexanes )2:3ꢀ.
Encouraged by this successful result, we have prepared
representative 3-acetoxymethylquinoline derivatives )7, 8ꢀ
from the Baylis-Hillman adducts )1f, gꢀ, obtained from the
substituted appropriate 2-nitrobenzaldehydes and alkyl
vinyl ketones )Scheme 3, Table 1ꢀ. A plausible mechanism
for the formation of 3-acetoxymethyl-)1Hꢀ-quinol-2-one
derivatives and 3-acetoxymethylquinoline derivatives from
the corresponding Baylis±Hillman adducts is described in
Schemes 2 and 3.
Table 1. Synthesis of functionalized )1Hꢀ-quinol-2-ones and quinolines
a
b
Product
Yield )%ꢀ
Mp )8Cꢀ
1
R
2
R
3
Substrate
R
c
1
1
1
1
1
1
1
a
b
c
d
e
f
H
H
H
H
OMe
OEt
OMe OMe OEt
3
77
89
72
87
63
83
56
167±169
167±169
177±178
182±183
94±95
c
3
4
5
OEt
H
H
OMe OEt
H
H
c
6
Me
Et
7
8
±
97±98
g
OMe OMe Me
All reactions were carried out on a 1 mmol scale of Baylis±Hillman adducts
1a±gꢀ with iron )6 mmolꢀ in the presence of acetic acid )5 mLꢀ at re¯ux for
0min. The products ) 3±5ꢀ were obtained as golden yellow crystalline
)
3
We have also prepared the interesting allylic alcohols,
3-hydroxymethyl-)1Hꢀ-quinol-2-one )3aꢀ and 3-hydroxy-
methyl-2-methylquinoline )6aꢀ, via the treatment of
3-acetoxymethyl-)1Hꢀ-quinol-2-one )3ꢀ and 3-acetoxy-
methyl-2-methylquinoline )6ꢀ, respectively, with aqueous
potassium carbonate/methanol )Schemes 2 and 3ꢀ.
solids after usual work-up followed by crystallization )chloroform and
hexanes, 1:1ꢀ and the products )6 and 8ꢀ were obtained as brown crystalline
solids after usual work-up followed by column chromatography )silica gel,
30% EtOAc in hexanesꢀ and crystallization )chloroform and hexanes, 2:3ꢀ.
The compound 7 was obtained as brown liquid after column chroma-
tography )silica gel, 30% EtOAc in hexanesꢀ.
a
1
13
All the products 3±8 gave satisfactory IR, H NMR )200 MHzꢀ, C NMR
50MHzꢀ spectral data and elemental analyses.
)
In conclusion, we have successfully synthesized 3-acetoxy-
methyl-)1Hꢀ-quinol-2-one derivatives and 2-alkyl-3-acetoxy-
methylquinoline derivatives from the Baylis±Hillman
adducts derived from alkyl acrylates and alkyl vinyl
b
Isolated yields of the pure products )for 3±5 after crystallization, for 6 and
after column chromatography followed by crystallization, for 7 after
column chromatographyꢀ.
8
c
Structure was also con®rmed by mass spectral analysis.

D.Basavaiah et al./ Tetrahedron 58 %2002) 3693±3697
3695
Scheme 3.
ketones, thus demonstrating the ef®cacy of Baylis±Hillman
adducts in organic synthesis.
71% yield )0.153 gꢀ, as golden yellow crystals. Mp: 167±
1698C; IR )KBrꢀ:1622, 1664, 1730, 2800±3200 )multiple
21 1
bandsꢀ cm ; H NMR: 2.17 )s, 3Hꢀ, 5.21 )s, 2Hꢀ, 7.18±
1
3
7
.62 )m, 4Hꢀ, 7.85 )s, 1Hꢀ, 11.39 )b, 1Hꢀ; C NMR: d
21.06, 61.54, 116.10, 119.71, 122.87, 127.67, 127.92,
30.72, 138.25, 138.55, 163.25, 170.86; MS )m/zꢀ: 217
1
. Experimental
1
1
1
.1. General
)M ꢀ; Analysis calcd for C12H11NO : C, 66.35; H, 5.10;
3
N, 6.45; found: C, 66.26; H, 5.12; N, 6.52.
Melting points were recorded on a Super®t )Indiaꢀ capillary
melting point apparatus and are uncorrected. IR spectra
were recorded on a JASCO-FT-IR model 5300 spectrometer
1.1.2. 3-ꢀAcetoxymethyl)-ꢀ1H)-quinol-2-one ꢀ3) [from
3-hydroxy-2-methylene-3-ꢀ2-nitrophenyl)pro-
methyl
1
using samples as neat liquids or as KBr plates. H NMR
panoate ꢀ1a)]. To a stirred solution of methyl 3-hydroxy-
2-methylene-3-)2-nitrophenylꢀpropanoate )1aꢀ )1 mmol,
0.237 gꢀ in acetic acid )5 mLꢀ at 1108C electrolytic iron
powder )6 mmol, 0.335 gꢀ was added and stirring continued
for 30min at same temperature. The reaction mixture was
cooled to room temperature and acetic acid removed under
reduced pressure. Then the reaction mixture was diluted
with ethyl acetate )15 mLꢀ and stirred for 2 min and ®ltered
to remove iron impurities. The insoluble iron residue was
washed with ethyl acetate )2£10mLꢀ. The ®ltrate and
washings were combined. Ethyl acetate was removed and
the solid obtained was crystallized from chloroform
and hexanes )1:1ꢀ to provide 3-acetoxymethyl-)1Hꢀ-
quinol-2-one )3ꢀ in 77% yield )0.167 gꢀ, as golden yellow
1
200 MHzꢀ and C NMR )50MHzꢀ spectra were recorded
3
)
in deuterochloroform )CDCl ꢀ or in DMSO-d on a Bruker-
3
6
AC-200 spectrometer using tetramethylsilane )TMS, dˆ0ꢀ
as internal standard. Mass spectra were recorded on a micro-
mass VG 7070H instrument. Elemental analyses were
recorded on a Perkin±Elmer 240C-CHN analyzer. All the
required Baylis±Hillman adducts )1a±dꢀ were obtained via
the reaction between alkyl acrylates and the corresponding
ortho-nitrobenzaldehydes in the presence of catalytic
amount of DABCO. Similarily the allylic alcohols )1e±gꢀ
were obtained by the coupling of )mꢀethyl vinyl ketone
with the corresponding ortho-nitrobenzaldehydes under
1
7,18,28
the catalytic in¯uence of DABCO in THF as a solvent.
1
13
crystals. Mp: 167±1698C. Spectral data )IR, H and
C
1
.1.1. 3-ꢀAcetoxymethyl)-ꢀ1H)-quinol-2-one ꢀ3) [from
NMRꢀ of this molecule are identical with that of the
molecule prepared from methyl 3-acetoxy-2-methylene-3-
)2-nitrophenylꢀpropanoate.
methyl 3-acetoxy-2-methylene-3-ꢀ2-nitrophenyl)propano-
ate ꢀ2a)]. To a stirred solution of methyl 3-acetoxy-2-
methylene-3-)2-nitrophenylꢀpropanoate )2aꢀ )1 mmol,
0
.279 gꢀ in acetic acid )5 mLꢀ at 1108C electrolytic iron
1.1.3. 3-ꢀAcetoxymethyl)-ꢀ1H)-quinol-2-one ꢀ3) [from
ethyl 3-hydroxy-2-methylene-3-ꢀ2-nitrophenyl)propano-
ate ꢀ1b)]. The reaction of ethyl 3-hydroxy-2-methylene-3-
)2-nitrophenylꢀpropanoate )1bꢀ with Fe/acetic acid )follow-
ing a similar procedure as mentioned for the reaction of the
allyl alcohol )1aꢀ with Fe/acetic acidꢀ provided 3-)acetoxy-
methylꢀ-)1Hꢀ-quinol-2-one )3ꢀ in 89% yield as golden
powder )6 mmol, 0.335 gꢀ was added and stirring continued
for 30min at the same temperature. The reaction mixture
was cooled to room temperature and acetic acid removed
under reduced pressure. The reaction mixture was diluted
with ethyl acetate )15 mLꢀ, stirred for 2 min and ®ltered to
remove iron impurities. The insoluble iron residue was
washed with ethyl acetate )2£10mLꢀ and combined with
the ®ltrate. Ethyl acetate was removed and the solid
obtained crystallized from chloroform and hexanes )1:1ꢀ
to provide 3-)acetoxymethylꢀ-)1Hꢀ-quinol-2-one )3ꢀ in
1
yellow crystals. Mp: 167±1698C. Spectral data )IR, H
1
3
and C NMRꢀ of this molecule are identical with that of
the molecule prepared from methyl 3-acetoxy-2-methylene-
3-)2-nitrophenylꢀpropanoate.

3696
D.Basavaiah et al./ Tetrahedron 58 %2002) 3693±3697
1.1.4. 3-ꢀAcetoxymethyl)-6,7-dimethoxy-ꢀ1H)-quinol-2-
one ꢀ4). Colorless crystals. Yield: 72%; mp: 177±1788C;
IR )KBrꢀ: 1620, 1658, 1745, 2800±3400 )multiple bandsꢀ
135.09, 144.58, 149.63, 152.85, 155.52, 170.79; Analysis
calcd for C H NO : C, 65.44; H, 6.22; N, 5.09; found:
C, 65.26; H, 6.17; N, 5.12.
1
5
17
4
2
1 1
cm ; H NMR: d 2.14 )s, 3Hꢀ, 3.93 )s, 3Hꢀ, 3.99 )s, 3Hꢀ,
.18 )s, 2Hꢀ, 6.79 )s, 1Hꢀ, 6.96 )s, 1Hꢀ, 7.79 )s, 1Hꢀ, 11.71
5
)
1.1.9. 3-ꢀHydroxymethyl)-ꢀ1H)-quinol-2-one ꢀ3a). A mix-
ture of 3-)acetoxymethylꢀ-)1Hꢀ-quinol-2-one )3ꢀ )0.5 mmol,
0.109 gꢀ, potassium carbonate )1.5 mmol, 0.207 gꢀ in
methanol )2 mLꢀ containing 1 drop of water was stirred at
room temperature for 1 h. The reaction mixture was ®ltered
off and the precipitate washed with methanol )4 mLꢀ. The
combined methanolic solution was concentrated and the
crude product obtained subjected to crystallization from
methanol at 08C to provide 3-)hydroxymethylꢀ-)1Hꢀ-
quinol-2-one )3aꢀ as yellow crystals in 85% yield
1
b, 1Hꢀ; C NMR: d 21.02, 56.06, 56.23, 61.51, 98.04,
3
1
1
07.67, 113.00, 124.04, 134.23, 138.51, 145.88, 152.64,
63.20, 170.85; Analysis calcd for C H NO : C, 60.65;
1
4
15
5
H, 5.45; N, 5.05; found: C, 60.41; H, 5.48; N, 5.00.
1
2
1
.1.5. 3-ꢀAcetoxymethyl)-7-ethoxy-6-methoxy-ꢀ1H)-quinol-
-one ꢀ5). Golden yellow crystalline solid. Yield: 87%; mp:
82±1838C; IR )KBrꢀ: 1624, 1662, 1741, 2750±3200
2
1
1
)
multiple bandsꢀ cm ; H NMR: d 1.54 )t, 3H,
2
1
Jˆ6.8 Hzꢀ, 2.15 )s, 3Hꢀ, 3.92 )s, 3Hꢀ, 4.21 )q, 2H,
)0.074 gꢀ. Mp: 199±2008C; IR )KBrꢀ: 1651, 3373 cm ;
1
Jˆ6.8 Hzꢀ, 5.19 )s, 2Hꢀ, 6.75 )s, 1Hꢀ, 6.96 )s, 1Hꢀ, 7.78
H NMR )DMSO-d
1H, Jˆ5.6 Hzꢀ, 7.11±7.55 )m, 3Hꢀ, 7.68 )d, 1H, Jˆ
6
ꢀ: d 4.40)d, 2H, Jˆ5.6 Hzꢀ, 5.22 )t,
1
3
s, 1Hꢀ, 10.92 )b, 1Hꢀ; C NMR: d 14.58, 21.04, 56.38,
)
1
3
6
1
1.63, 64.93, 99.15, 108.56, 113.08, 124.32, 134.49,
38.71, 146.40, 152.45, 163.30, 170.85; Analysis calcd for
7.8 Hzꢀ, 7.85 )s, 1Hꢀ, 11.78 )b, 1Hꢀ; C NMR )DMSO-
ꢀ: d 58.70, 115.14, 119.53, 121.96, 127.69, 129.53,
d
6
1
C H NO : C, 61.85; H, 5.88; N, 4.81; found: C, 62.12; H,
1
133.89, 134.19, 137.90, 161.47; MS )m/zꢀ: 175 )M ꢀ;
Analysis calcd for C10 NO : C, 68.56; H, 5.18; N, 8.00;
found: C, 68.76; H, 5.15; N, 7.96.
5
17
5
5
.84; N, 4.85.
H
9
2
1.1.6. 3-ꢀAcetoxymethyl)-2-methylquinoline ꢀ6). To a
stirred solution of 4-hydroxy-3-methylene-4-)2-nitro-
1.1.10. 3-ꢀHydroxymethyl)-2-methylquinoline ꢀ6a).
Brown crystals )crystallized from acetonitrile at 08Cꢀ.
phenylꢀbutan-2-one )1eꢀ )1 mmol, 0.221 gꢀ in acetic acid
)
2
1
5 mLꢀ at 1108C electrolytic iron powder )6 mmol,
.335 gꢀ was added and stirring was continued for 30 min
Yield: 80%; mp: 139±1418C; IR )KBrꢀ: 1657, 3429 cm ;
1
0
H NMR )DMSO-d
1Hꢀ, 7.48±7.71 )m, 2Hꢀ, 7.86±7.98 )m, 2Hꢀ, 8.20)s, 1Hꢀ;
ꢀ: d 2.60)s, 3Hꢀ, 4.69 )s, 2Hꢀ, 5.45 )b,
6
at same temperature. The reaction mixture was cooled to
room temperature and acetic acid was removed under
reduced pressure. Then the reaction mixture was diluted
with ethyl acetate )15 mLꢀ and stirred for 2 min, ®ltered
to remove iron impurities. The insoluble iron residue was
washed with ethyl acetate )2£10mLꢀ. The ®ltrate and
washings were combined. Ethyl acetate was removed and
the residue thus obtained was puri®ed by column chroma-
tography )silica gel, 30% EtOAc in hexanesꢀ followed by
crystallization )chloroform and hexanes )2:3ꢀꢀ to afford
1
3
C NMR )DMSO-d
127.72, 128.11, 128.87, 132.65, 134.54, 146.43, 157.52;
Analysis calcd for C11 11NO: C, 76.28; H, 6.40; N, 8.09;
found: C, 76.12; H, 6.35; N, 8.15.
ꢀ: d 22.41, 60.71, 125.84, 126.99,
6
H
Acknowledgements
We thank DST )New Delhiꢀ for funding this project. We
also thank the UGC )New Delhiꢀ for the Special Assistance
Program in Organic Chemistry in the School of Chemistry,
University of Hyderabad, Hyderabad. R. M. R. thanks CSIR
)New Delhiꢀ and N. K., D. S. S. thank UGC )New Delhiꢀ for
their research fellowships.
3
)
-)acetoxymethylꢀ-2-methylquinoline )6ꢀ in 63% yield
0.135 gꢀ, as brown crystals. Mp: 94±958C; IR )KBrꢀ:
21 1
620, 1738 cm ; H NMR: d 2.16 )s, 3Hꢀ, 2.76 )s, 3Hꢀ,
.29 )s, 2Hꢀ, 7.45±7.56 )m, 1Hꢀ, 7.66±7.85 )m, 2Hꢀ, 8.03 )d,
1
5
1
6
1
1
3
H, Jˆ8.2 Hzꢀ, 8.09 )s, 1Hꢀ; C NMR: d 20.85, 22.84,
3.85, 126.05, 126.63, 127.46, 127.67, 128.40, 129.66,
36.01, 147.42, 157.73, 170.58; MS )m/zꢀ: 215 )M ꢀ;
1
Analysis calcd for C H NO : C, 72.54; H, 6.09; N, 6.51;
1
References
3
13
2
found: C, 72.49; H, 6.05; N, 6.58.
1
. Leclerc, G.; Marciniak, G.; Decker, N.; Schwartz, J. J.Med.
Chem. 1986, 29, 2427±2432.
1.1.7. 3-ꢀAcetoxymethyl)-2-ethylquinoline ꢀ7). Brown
liquid. Yield: 83%; IR )neatꢀ: 1624, 1741 cm ; H NMR:
2
1 1
2. Leclerc, G.; Marciniak, G.; Decker, N.; Schwartz, J. J.Med.
Chem. 1986, 29, 2433±2438.
d 1.44 )t, 3H, Jˆ7.2 Hzꢀ, 2.15 )s, 3Hꢀ, 3.13 )q, 2H, Jˆ
7
2
6
1
.2 Hzꢀ, 5.33 )s, 2Hꢀ, 7.48±7.62 )m, 1Hꢀ, 7.71±7.87 )m,
3. Kazuo, B.; Takafumi, F.; Yasuo, O.; Kazuyuki, N. Ger. Offen.;
3,034,237, 1981; Chem.Abstr. 1981, 95, 80755z.
4. Otsuka Pharmaceutical Co. Ltd. Jpn. Kokai Tokyo Koho Jp 59
29,668, 1984; Chem.Abstr. 1984, 101, 72628n.
5. Pettit, G. R.; Kalnins, M. V. J.Org.Chem. 1960, 25, 1365±
1367.
1
3
Hꢀ, 8.20±8.29 )m, 2Hꢀ; C NMR: d 13.46, 20.94, 28.70,
3.61, 126.13, 126.59, 127.23, 127.50, 128.40, 129.75,
36.78, 147.41, 162.30, 170.67; Analysis calcd for
C H NO : C, 73.34; H, 6.59; N, 6.11; found: C, 73.55;
2
1
4
15
H, 6.66; N, 6.15.
6
. Michael, J. P. Nat.Prod.Rep. 1997, 14, 605.
1.1.8. 3-ꢀAcetoxymethyl)-6,7-dimethoxy-2-methylquino-
line ꢀ8). Brown crystalline solid. Yield: 56%; mp: 97±
7. Balasubramanian, M.; Keay, J. G. Comprehensive Hetero-
cyclic Chemistry II; Katritzky, A. R., Rees, C. W., Scriven,
E. F. V., Eds.; Pergamon: Oxford, 1996; Vol. 5, pp. 245±300.
8. Jones, G. Comprehensive Heterocyclic Chemistry II;
Katritzky, A. R., Rees, C. W., Scriven, E. F. V., Eds.; Perga-
mon: Oxford, 1996; Vol. 5, pp. 167±243.
2
1
1
88C; IR )KBrꢀ: 1620, 1736 cm ; H NMR: d 2.14 )s,
9
3
7
2
Hꢀ, 2.70 )s, 3Hꢀ, 4.00 )s, 3Hꢀ, 4.03 )s, 3Hꢀ, 5.25 )s, 2Hꢀ,
.03 )s, 1Hꢀ, 7.37 )s, 1Hꢀ, 7.94 )s, 1Hꢀ; C NMR: d 20.96,
2.51, 56.09, 56.19, 64.21, 105.19, 107.44, 122.10, 125.85,
1
3

D.Basavaiah et al./ Tetrahedron 58 %2002) 3693±3697
3697
9
. Cho, C. S.; Oh, B. H.; Shim, S. C. Tetrahedron Lett. 1999, 40,
499±1500.
21. Trost, B. M.; Tsui, H.-C.; Toste, F. D. J.Am.Chem.Soc. 2000,
122, 3534±3535.
1
1
0. Cacchi, S.; Fabrizi, G.; Marinelli, F. Synlett 1999, 401±404.
1. Cho, C. S.; Oh, B. H.; Kim, J. S.; Kim, T.-J.; Shim, S. C.
Chem.Commun. 2000, 1885±1886.
22. Basavaiah, D.; Reddy, R. M. Tetrahedron Lett. 2001, 42,
3025±3027.
1
23. Chamak, A.; Amri, H. Tetrahedron Lett. 1998, 38, 375±378.
24. Familoni, O. B.; Kaye, P. T.; Klaas, P. J. Chem.Commun.
1998, 2563±2564.
1
1
1
1
1
1
1
1
2
2. Arcadi, A.; Cacchi, S.; Fabrizi, G.; Manna, F.; Pace, P. Synlett
1
998, 446±448.
3. Kobayashi, K.; Kitamura, T.; Yoneda, K.; Morikawa, O.;
Konishi, H. Chem.Lett. 2000, 798±799.
25. Kim, J. N.; Lee, K. Y.; Kim, H. S.; Kim, T. Y. Org.Lett. 2000,
2, 343±345.
4. Basavaiah, D.; Sreenivasulu, B.; Srivardhanarao, J.
Tetrahedron Lett. 2001, 42, 1147±1149.
26. Kim, J. N.; Lee, H. J.; Lee, K. Y.; Kim, H. S. Tetrahedron Lett.
2001, 42, 3737±3740.
5. Basavaiah, D.; Bakthadoss, M.; Pandiaraju, S. Chem.
Commun. 1998, 1639±1640.
6. Drewes, S. E.; Roos, G. H. P. Tetrahedron 1988, 44, 4653±
27. Transformation of nitro group into amino group with the
reagent, Fe/acetic acid, is well documented in the literature,
see Refs. 29±32.
4
670.
7. Basavaiah, D.; Dharmarao, P.; Suguna Hyma, R. Tetrahedron
996, 52, 8001±8062.
28. Basavaiah, D.; Gowriswari, V. V. L. Tetrahedron Lett. 1986,
27, 2031±2032.
1
29. Bunce, R. A.; Herron, D. M.; Ackerman, M. L. J.Org.Chem.
2000, 65, 2847±2850.
30. Quallich, G. J.; Morrissey, P. M. Synthesis 1993, 51±53.
8. Ciganek, E. Organic Reactions; Paquette, L. A., Ed.; Wiley:
New York, 1997; Vol. 51, pp. 201±350.
9. Hoffman, H. M. R.; Rabe, J. J.Org.Chem. 1985, 50, 3849±
31. Hazlet, S. E.; Dornfeld, C. A. J.Am.Chem.Soc.
1781±1782.
1944, 66,
3859.
0. Basavaiah, D.; Kumaragurubaran, N.; Sharada, D. S.
Tetrahedron Lett. 2001, 42, 85±87.
32. Wertheim, E. Organic Synthesis, 1943; Collect. Vol. No. 2, pp
471±473.