110
M A Nasseri et al.
TLC on silica-gel polygram SILG/UV 254 plates. 2.3b Compound (3i): methyl-6-chloro-2-methyl-4-
Melting points were determined in electrothermal 9100 phenyl-3-quinolinecarboxylat: Yellow solid, m.p 135◦C,
system open capillaries and were uncorrected. IR spec- (Lit [41] 135◦C), IR (KBr, cm−1): υ: 3035, 2958, 2900,
tra were taken on a Perkin Elmer 781 spectrometer in 1749, 1561, 1455, 1402, 1297, 1237, 1182, 1070, 872,
1
KBr pellets and reported in cm−1. NMR spectra were 767. H NMR (400 MHz, CDCl3): δ 2.74 (s, 3H),
measured on a Bruker DPX 250 MHz spectrometer in 3.56 (s, 3H), 7.25–8.01 (c, 8H). 13C NMR (62.9 MHz,
DMSO-d6 with chemical shift given in ppm relative to CDCl3) δ 23.7, 52.2, 125.2, 125.8, 128.0, 128.5, 128.8,
TMS as internal standard.
129.1, 130.5, 131.2, 132.4, 134.9, 145.5, 146.1, 145.9,
154.9, 168.6. MS(m/z, %): 313(M +2, 31), 311(M+,
100), 296(6), 281(50), 279(97), 254(14), 251(16),
236(4), 211(10), 189(34), 175(52), 108(37), 94(33),
74(17).
2.2 Preparation of PEG-SO3H
To a magnetically stirred mixture of 6.00 g (1 mmol)
of Poly(ethylene glycol) (PEG-6000) in 10 mL of
dichloromethane, 0.67 mL of chlorosulphonic acid
(10 mmol) was added drop-wise at 0◦C during 1 h. HCl
gas was removed from the reaction vessel immedi-
ately and the mixture was stirred for 12 h. The mix-
ture was filtered and washed with 20 mL of diethylether
and dried at room temperature to afford 5.10 g of PEG-
SO3H as a white powder. The number of H+ sites on
the PEG–SO3H was determined by acid–base titration
to be 0.5 meq/g.
2.3c Compound (3x): 2-Chloro-11-phenyl-7,8,9,10-
tetrahydro-6H-cyclohepta[b]quinoline: Yellow solid,
m.p 195◦C, (Lit [42] 195◦C), IR (KBr, cm−1): υ: 3080,
3050, 2930, 2850, 1615, 1600, 1500, 1470, 1360, 1180,
1
990, 870, 820, 680, H NMR (400 MHz, CDCl3): δ:
1.60 (s, 2H), 1.84 (s, 4H), 2.68 (c, 2H) 3.26 (c, 2H),
7.22–7.96 (c, 8H).13C NMR (62.9 MHz, CDCl3) δ26.9,
28.4, 30.7, 31.8, 40.1, 125.1, 127.7, 127.9, 128.6, 129.0,
129.3, 130.3, 131.3, 134.8, 136.9, 144.2, 144.7, 165.1,
MS (m/z, %): 308((M+2)−1, 33), 306(M-1, 100),
292(9), 280 (15), 277(12), 252(13), 242(17), 228(18),
215(18) ,201(10), 188(10), 127(23), 120(25), 107(15).
2.3 General procedure for the preparation
of quinoline derivatives
2.3d Compound (3ee): 6-Chloro-2,4-diphenylquinoline:
Yellow solid mp: 206◦C, (Lit. [42] 208◦C), IR (KBr,
cm−1): υ: 3019, 2985, 1580, 1508, 1465, 1355, 1150,
To a mixture of carbonyl compounds (1.0 mmol) and 2-
amino-5-chlorobenzophenone or 2-aminobenzophenone
(1.0 mmol) was added PEG-SO3H (0.2 g) in H2O
(3 mL). The mixture was stirred at 60◦C for appropri-
ated reaction time (table 3). The progress of the reaction
was monitored by TLC. After completion of the reac-
tion, the precipitated solid was filtered and washed with
water. The crude solid product was crystallized from
EtOH to afford the pure quinoline product in high purity
in excellent yield. Structural assignments of the prod-
ucts are based on their 1H NMR, 13C NMR, MS and IR
spectra.
1
1005, 840, 790, 755. H NMR (400 MHz, CDCl3): δ:
7.25–8.19 (c, 14H),13C NMR (62.9 MHz, CDCl3) δ
120.5, 124.5, 126.5, 127.5, 128.7, 128.8, 128.9, 129.4,
129.6, 130.4, 131.7, 132.2, 137.5, 139.2, 147.2, 148.4,
157.1, MS(m/z, %): 316(M +2, 43), 314(M+, 100),
280(27), 277(18), 250(6), 236(7), 201(17), 175(13),
139(57), 125(19).
3. Results and discussion
The supported acidic PEG catalyst was prepared via
anchoring chlorosulphonic acid onto polyethylene gly-
col. This polymeric catalyst was used as an efficient
Brönsted acid for different organic functional group
transformations either as reagent or as catalyst under
heterogeneous and homogenous. The catalyst can easily
be prepared from the readily available reagents, chloro-
sulphonic acid and poly ethylene glycol to give PEG
modified sulphuric acid (scheme 1).
2.3a Compound (3c): 7-chloro-9-phenyl-3,4-dihydro-
1-2H-acridinone: Yellow solid, m.p 184◦C (Lit [41]
185◦C), IR (KBr, cm−1)νmax 3024, 2975, 2870, 1698,
1549, 1476, 1380, 1210, 1075, 1007, 970, 838, 697. 1H
NMR (400 MHz, CDCl3)δ 2.26 (q, 2H, J = 6.4 Hz),
2.72 (t, 2H, J = 6.4 Hz), 3.37 (t, 2H, J = 6.4 Hz),
7.17 (t, 2H), 7.42 (s, 1H), 7.53 (m, 3H), 7.69 (d,
1H, J = 8.8 Hz), 8.01 (d, 1H, J = 8.8 Hz), MS (m/z,
%): 308((M +2)−1, 34), 306 (M −1, 100), 281(5),
280 (29), 278(15), 253(4), 244(10), 215(27), 188(12) ,
153(17), 120(20), 107(15).
In order to evaluate the catalytic efficiency of PEG–
SO3H and to determine the most appropriate reaction
conditions, initially a model study was carried out on