N.-A. Mohsin et al.
1
H, ArH), 7.77 (d, J = 8.4 Hz, 2H, ArH) ppm; C NMR
3
2
6), 165.62 (C-4), 167.91 (C=O) ppm; IR (KBr): mꢀ = 2975,
1691, 1655, 1596, 1463, 1435, 1373, 1351, 1324, 1271,
1224, 1141, 1125, 1104, 983, 896, 859, 844, 832, 810, 768,
(
(
(
(
DMSO-d , 100 MHz): d = 23.76 (2CH ), 24.23, 24.28
6
3
(CH ) ), 41.60 (C-3), 51.84 (N(CH ) ), 58.46 (C-2), 96.08
2
2
2 2
-
1
C-5), 129.15, 132.03 (ArC), 132.47, 138.14 (ArC ), 150.33
q
661 cm ; UV (CH OH): k (loge) = 206 (4.272), 332
3
?
(4.266) nm; HRMS (EI ): m/z calcd. C H Cl N O
C-6), 165.98 (C-4), 170.68 (CON) ppm; IR (KBr): mꢀ = 2947,
1
8
20
2 2
?
1
694, 1619, 1574, 1467, 1350, 1261, 1222, 1171, 1118, 1093,
([M-HCl] ) 350.0953, found 350.0964.
-[1-(3,4-Dichlorobenzoyl)-1,2,3,4-tetrahydro-2,2-dime-
thylpyridin-4-ylidene]piperidinium chloride
25b, C H Cl N O)
-1
9
88, 896, 841, 760, 671 cm ; UV (CH OH): k (loge) = 336
3
1
?
4.446), 205 (4.228) nm; HRMS (EI ): m/z calcd. C H
(
18 21-
?
ClN O ([M-HCl] ) 316.1342, found 316.1353.
2
(
1
9
23
3 2
1
-[1-(4-Chlorobenzoyl)-1,2,3,4-tetrahydro-2,2-dimethyl-
pyridin-4-ylidene]piperidinium chloride
24b, C H Cl N O)
Reaction of 1.86 g of 18b (5.8 mmol) with 1.95 g of 3,4-
3
dichlorobenzoyl chloride (9.3 mmol) in 10 cm of dry
(
dichloromethane gave a precipitate which was dissolved in
ethanol, treated with charcoal, filtered, evaporated, and
recrystallized from acetone. Yield: 236 mg (10%) of 25b
1
9
24
2 2
Reaction of 1.76 g of 18b (5.5 mmol) with 1.54 g of 4-
3
chlorobenzoyl chloride (8.8 mmol) in 12 cm of dry
dichloromethane gave a precipitate which was dissolved
in ethanol, treated with charcoal, filtered, evaporated, and
recrystallized from acetone. Yield: 250 mg (12%) of 24b
as
white
crystals.
Rf = 0.41
(CHCl :ben-
3
1
zene:MeOH:DEA = 4:4:1:0.25); m.p.: 185 °C; H NMR
(DMSO-d , 400 MHz): d = 1.62 (s, 6H, 2CH ), 1.75 (br,
6H, (CH ) ), 3.37 (s, 2H, H-3), 3.99–4.03 (m, 4 H,
6
3
as
white
crystals.
Rf = 0.42
(CHCl :ben-
3
2 3
1
zene:MeOH:DEA = 4:4:1:0.25); m.p.: 194 °C; H NMR
(NCH ) ), 6.10 (d, J = 8.4 Hz, 1H, H-5), 7.45 (d,
2
2
(
DMSO-d , 400 MHz): d = 1.57 (s, 6H, 2CH ), 1.75 (br, s,
J = 8.4 Hz, 1H, H-6), 7.65 (dd, J = 8.4, 1.8 Hz, 1H,
ArH), 7.75 (d, J = 8.4 Hz, 1H, ArH), 7.85 (d, J = 1.8 Hz,
6
3
6
H, (CH ) ), 3.43 (s, 2H, H-3), 4.01 (br, 4H, 2NCH ), 6.11
2 3 2
1
3
(
d, J = 8.1 Hz, 1H, H-5), 7.60 (d, J = 8.1 Hz, 1H, H-6),
.66 (d, J = 8.4 Hz, 2H, ArH), 7.80 (d, J = 8.8 Hz, 2H,
1H, ArH) ppm;
C NMR (DMSO-d , 100 MHz):
6
7
d = 22.88 (CH ), 24.04 (2CH ), 26.84, 27.31 (2CH ),
40.10 (C-3), 51.89 (N(CH ) ), 58.56 (C-2), 96.58 (C-5),
2 2
2
3
2
1
3
ArH) ppm; C NMR (DMSO-d , 100 MHz): d = 22.97
6
(
CH ), 23.55 (2CH ), 26.81, 27.39 (2CH ), 39.97 (C-3),
2
128.43, 130.00, 131.91 (ArC), 131.72, 132.21, 136.88
3
2
5
1.49 (N(CH ) ), 58.46 (C-2), 94.63 (C-5), 129.14, 132.05
2
(ArC ), 148.82 (C-6), 166.93 (C-4), 167.62 (C=O) ppm; IR
q
2
(
ArC), 132.35, 138.15 (ArC ), 150.73 (C-6), 167.09 (C-4),
q
(KBr): mꢀ = 2982, 2940, 1704, 1614, 1578, 1477, 1462,
1366, 1333, 1291, 1257, 1223, 1189, 1162, 1123, 1104,
1
1
1
70.45 (C=O) ppm; IR (KBr): mꢀ = 2942, 1696, 1573, 1461,
351, 1335, 1288, 1251, 1229, 1207, 1171, 1112, 1089,
-
1
1018, 985, 903, 846 cm ; UV (CH OH): k (loge) = 207
3
-
1
?
(4.340), 333 (4.322) nm; HRMS (EI ): m/z calcd. C H
018, 986, 899, 760, 694 cm
;
UV (CH OH):
3
19 22-
?
?
Cl N O ([M-HCl] ) 364.1109, found 364.1114.
k (loge) = 339 (4.475), 205 (4.233) nm; HRMS (EI ):
m/z calcd. C H ClN O ([M-HCl] ) 330.1499, found
2
2
?
1
9
23
2
1-[1,2,3,4-Tetrahydro-2,2-dimethyl-1-(2-phenyl-
3
30.1508.
acetyl)pyridin-4-ylidene]piperidinium chloride
1
-[1-(3,4-Dichlorobenzoyl)-1,2,3,4-tetrahydro-2,2-di-
(26b, C H ClN O)
2
2
0
27
methylpyridin-4-ylidene]pyrrolidinium chloride
25a, C H Cl N O)
Reaction of 1.78 g of 18a (5.8 mmol) with 1.55 g of 3,4-
Reaction of 1.29 g of 18b (4.02 mmol) with 995 mg of 2-
3
phenylacetyl chloride (6.4 mmol) in 10 cm of dry
(
1
8
21
3 2
dichloromethane gave a residue which crystallized from
acetone/ethyl acetate. The precipitate was dissolved in hot
ethanol, treated with charcoal, filtered, evaporated, and
recrystallized from acetone/ethyl acetate. Yield: 240 mg
(17%) of 26b as white crystals. R = 0.45 (CHCl :ben-
3
chlorobenzoyl chloride (7.4 mmol) in 10 cm of dry
dichloromethane gave a precipitate which was dissolved
in ethanol, treated with charcoal, filtered, evaporated, an
recrystallized from acetone. Yield: 283 mg (13%) of 25a as
f
3
1
white
crystals.
Rf = 0.14
(CHCl :ben-
3
zene:MeOH:DEA = 4:4:1:0.25); m.p.: 170 °C; H NMR
(DMSO-d , 400 MHz): d = 1.44 (s, 6H, 2CH ), 1.71 (br,
6H, (CH ) ), 3.13 (s, 2H, H-3), 3.92–3.97 (m, 4H,
1
zene:MeOH:DEA = 4:4:1:0.25); m.p.: 205 °C; H NMR
6
3
(
DMSO-d , 400 MHz): d = 1.64 (s, 6H, 2CH ), 2.04 (br,
6
3
2 3
4
H, (CH ) ), 3.28 (s, 2H, H-3), 3.87 (br, 2H, NCH ), 3.99
2
((NCH ) ), 4.17 (s, 2H, ArCH ), 6.10 (d, J = 8.1 Hz,
2 2
2
2
2
(
br, 2H, NCH ), 5.81 (d, J = 8.1 Hz, 1H, H-5), 7.47 (d, J =
2
1H, H-5), 7.24–7.33 (m, 5H, ArH), 8.25 (d, J = 8.4 Hz,
1
3
8
.1 Hz, 1H, H-6), 7.65 (dd, J = 8.2, 1.6 Hz, 1H, ArH),
.75 (d, J = 8.4 Hz, 1H, ArH), 7.84 (d, J = 1.5 Hz, 1H,
1H, H-6) ppm;
C NMR (DMSO-d6, 100 MHz):
7
d = 22.97 (CH ), 24.20 (2CH ), 26.82, 27.29 (2CH ),
2
3
2
1
3
ArH) ppm; C NMR (DMSO-d , 100 MHz): d = 24.18,
40.38 (C-3), 41.74 (ArCH ), 51.45, 51.55 (N(CH ) ), 58.05
2 2 2
6
2
4.22 ((CH ) ), 24.32 (2CH ), 41.74 (C-3), 52.14, 52.18
2
(C-2), 94.84 (C-5), 127.11, 128.66, 129.56 (ArC), 134.42
2
3
(
N(CH ) ), 58.51 (C-2), 97.99 (C-5), 128.45, 129.96,
2
(ArC ), 149.36 (C-6), 166.65 (C-4), 172.67 (C=O) ppm; IR
q
2
1
31.98 (ArC), 131.64, 132.33, 136.86 (ArC ), 148.47 (C-
q
(KBr): mꢀ = 2945, 1721, 1579, 1456, 1360, 1322, 1248,
1
23