Alcano 2

586 J. CHEM.
RESEARCH (S), 1998
Rapid Side-chain Chlorination of Heterocyclic J. Chem. Research (S),

1998, 586±587$
Compounds using Focused Microwave Irradiation$
Mazaahir Kidwai,* Seema Kohli and Parven Kumar
Department of Chemistry, University of Delhi, Delhi-110007, India
Rapid chlorination of side-chain Me groups of substituted quinolines and 2-mercapto-5-methyl 1,3,4-oxadiazole/

thiadiazole is reported using sodium hypochlorite under microwave irradiation.
Presently there is considerable interest in the rapid synthesis

of a variety of heterocyclic compounds under micro-
wave irradiation in domestic microwave ovens1 owing to
substantial reduction in reaction times. Halogenoarenes are
useful intermediate for industrial as well as laboratory
purposes.2 In continuation of our earlier work on micro-
wave reactions3±6 we report herein sodium hypochlorite as a
selective and cheap reagent for chlorination of side-chain
Me groups of 2-hydroxy-4-methyl-2-chloro-4-methyl- and
2-¯uoro-4-methyl-quinoline, 2-chloro-4-methylquinoline-3-
carbaldehyde and 2-mercapto-5-methyl-1,3,4-oxadiazole/
thiadiazole.
2-Hydroxy-4-methylquinoline was prepared7 by the
cyclisation of acetoacetanilide using sulfuric acid; this on
treatment with PCl5±POCl3 aorded 2-chloro-4-methyl-
quinoline which on reaction with potassium ¯uoride in
acetonitrile as a solvent gave 2-¯uoro-4-methylquinoline.
2-Chloro-4-methylquinoline-3-carbaldehyde and 2-mercapto-
5-methyl-1,3,4-oxadiazole/thiadiazole were prepared accord- Scheme 1
ing to literature methods.8,9
The chlorination of side-chain Me groups of substi-
tuted quinolines and 2-mercapto-5-methyl-1,3,4-oxadiazole/ Experimental
thiadiazole has been carried out using microwave irradiation Physical data for the new compounds are listed in Table 1.
(Scheme 1). The reaction involves free radical mono- Mps (uncorrected) were recorded on an electrothermal apparatus.
halogenation10 without aecting other substituents. All the IR (KBr) were recorded on a Model 599 Perkin-Elmer spectro-
synthesized compounds except 2b11 are new and are char- photometer and 1H NMR were recorded on a Hitachi R-600 FT
spectrophotometer using SiMe4 as internal standard. Mass spectra
acterised by physical and spectral data. 1H NMR of com- were recorded on a JEOL-JMS-DX 303 mass spectrophotometer.
pounds 1e,f showed a signal at d 13.25 due to SH which Spectral data for the new compounds are listed in Table 2. The
was exchangeable with D2O indicating that the compounds purities of the compounds were checked on silica coated A1 plates
are not dehydrodimerised at sulfur. Quinoline 1a and its (Merck).
chlorination product 2a exist in the hydroxy tautomeric General procedure for the chlorination of side-chain methyl groups
form and a peak at d 5.00 con®rms the presence of OH. of various substituted quinolines and 2-mercapto-5-methyl-1,3,4-
oxadiazole/thiadiazole.ÐTo a solution of 5±8 ml sodium hypo-
The domestic multimode microwave oven con®nes the chlorite (0.03 mol) in a 100 ml conical ¯ask were added appropriate
microwaves to the reaction vessel only and excess micro- substituted quinolines or 2-mercapto-5-methyl-1,3,4-oxadiazole/
waves are absorbed by a dummy load,12 hence leading to thiadiazole (0.01 mol). The reaction mixture was placed under
focused microwaves. focused microwaves in an unmodi®ed domestic microwave oven at
Table 1 Physical data for the new compounds

Elemental analysis [Found (calc.) %]
Compound Formula % Yield (time/min) C H N Mp
2a C10H8ClNO 92 (2.0) 62.04 4.18 7.26 150
(62.01) (4.13) (7.23)
2b C10H7Cl2N 93 (2.5) 56.63 3.28 6.57 83
(56.60) (3.30) (6.60)
2c C10H7ClFN 96 (2.3) 61.40 3.54 7.20 60
(61.38) (3.58) (7.16)
2d C11H7Cl2NO 90 (2.5) 54.80 2.93 5.81 120
(55.00) (2.91) (5.83)
2e C3H3ClN2SO 95 (1.3) 23.94 2.00 18.57 230
(23.92) (1.99) (18.60)
2f C3H3ClN2S2 89 (1.5) 21.60 1.76 16.80 220
(21.62) (1.80) (16.81)
2450 MHz. A dummy load of water was also introduced. TLC was
*To receive any correspondence. run every 30 s to check the progress of the reaction. Once the reac-
$This is a Short Paper as de®ned in the Instructions for Authors, tion was complete the reaction mixture was poured into water. The
Section 5.0 [see J. Chem. Research (S), 1998, Issue 1]; there is there- solid obtained was ®ltered o, washed with water and dried to give
fore no corresponding material in J. Chem. Research (M). the product.
J. CHEM. RESEARCH (S), 1998 587
Table 2 Spectral data for the new compounds

Compound IR (max/cmÿ1) 1
H NMR (d)
2a 790 (C ± Cl), 3400 (OH) 2.95 (s, 2 H, 4-CH2Cl), 5.00 (br, 1 H, OH), 7.00±7.90 (m, 5 H, Ar-H)
2b 795 (C ± Cl) 2.96 (s, 2 H, 4-CH2Cl), 7.12±8.0 (m, 5 H, Ar-H)
2c 790 (C ± Cl) 2.96 (s, 2 H, 4-CH2Cl), 7.10±8.02 (m, 5 H, Ar-H)
2d 795 (C ± Cl), 1680 (CO str.) 3.08 (s, 2 H, 4-CH2Cl), 7.25±8.35 (m, 4 H, Ar-H), 10.35 (s, 1 H, CHO)
2e 795 (C ± Cl), 1520 (C.N) 2.96 (s, 2 H, 5-CH2Cl), 13.2 (s, 1 H, 2-SH)
2f 790 (C ± Cl), 1530 (C.N) 2.94 (s, 2 H, 5-CH2Cl), 13.2 (s, 1 H, 2-SH)
Received, 27th April 1998; Accepted, 5th June 1998 6 M. Kidwai, K. R. Bhushan, P. Kumar and R. Kumar, Monatsh.
Paper E/8/03130D Chem., 1997, 128, 1291.
7 M. Kidwai, Chem. Educ., 1993, 4, 55.
8 O. Meth-Cohn, B. Narine and B. Tarnowski, J. Chem. Soc.,
References Perkin Trans 1, 1981, 1520.
1 S. Caddick, Tetrahedron, 1995, 51, 10403. 9 M. Kidwai, R. Kumar and Y. Goel, Main Group Met. Chem.,
2 Speciality Chemicals, ed. B. Pearson, Elsevier Applied Science, 1997, 20, 367.
London, 1991, pp. 15±93. 10 S. Futamura and Z. M. Zong, Bull. Chem. Soc. Jpn., 1992, 65,
3 M. Kidwai and P. Kumar, J. Chem. Res. (S ), 1996, 254. 345.
4 M. Kidwai, P. Kumar and S. Kohli, J. Chem. Res. (S ), 1997, 11 K. Otsubo, S. Morita, M. Uchida, K. Yamasaki, T. Kanbe and
24. T. Shimizu, Chem. Pharm. Bull., 1991, 39, 2906.
5 M. Kidwai, S. Kohli and P. Kumar, J. Chem. Res. (S ), 1998, 12 M. Kidwai, P. Kumar, Y. Goel and K. Kumar, Indian J. Chem.
52. Sect. B, 1997, 36, 175.

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586 J. CHEM.

RESEARCH (S), 1998

Rapid Side-chain Chlorination of Heterocyclic J. Chem. Research (S),

Rapid chlorination of side-chain Me groups of substituted quinolines and 2-mercapto-5-methyl 1,3,4-oxadiazole/

Presently there is considerable interest in the rapid synthesis

Table 1 Physical data for the new compounds

Table 2 Spectral data for the new compounds

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