1,2,4,6-SUBSTITUTED PYRIDINIUM DERIVATIVES - SYNTHESIS AND PROPERTIES

Full text of DOI:10.1135/cccc19942545

New Compounds
2545
1,2,4,6-SUBSTITUTED PYRIDINIUM DERIVATIVES – SYNTHESIS
AND PROPERTIES
Jiri URBAN* and Jiri VOLKE
The J. Heyrovsky Institute of Physical Chemistry,
Academy of Sciences of the Czech Republic, 182 23 Prague 8, The Czech Republic
Received April 27, 1994
Accepted August 20, 1994
In relation to the investigation of their electrochemical properties1,2,3 we prepared 24
pyridinium derivatives (I, IV, V, VI, VII) with alkyl and aryl substituents in positions 1,
2, 4 and 6, and 19 derivatives with two pyridinium nuclei (II, III, VIII, IX, X) connected
by an aliphatic or an aromatic chain.
All the compounds were prepared from the corresponding pyrylium derivatives by
reacting them with primary amines. The pyrylium derivatives were synthesized by
aldolization and acylation followed by cyclization leading to a heteroaromatic pyrylium
system4–7. In nucleophilic reactions with amines, the pyrylium derivatives yield pyridi-
nium derivatives. The reaction was performed by adding the corresponding amine to an
ethanolic suspension of the starting pyrylium salt8,9
.
Compounds with two pyridinium rings in the molecule were prepared by a similar
procedure. The synthesis of a substance of the general formula XI by reaction with an
excess of the diamine was found to be more convenient. This first step was followed by
reaction with the equimolar amount of the starting pyrylium salt. This procedure was
necessary for compounds with nonequally substituted pyridinium nuclei.
* The author to whom correspondence should be addressed.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

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Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2547
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Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2549
TABLE I
Physical characteristics of the pyridinium salts I – X
Calculated/Found
Formula
M.w.
M.p., °C
Yield, %
Compound
% C
% H
% Cl
% N
Ie
C27H26ClNO4
464.0
232 – 234
69.89
70.14
5.66
5.47
7.64
7.87
3.02
2.99
85
If
C28H28ClNO4
478.0
215 – 218
70.34
70.41
5.92
6.08
7.42
7.31
2.93
2.82
90
Ij
C30H23Cl2NO4
532.4
148 – 151
67.67
67.42
4.36
4.51
13.32
13.11
2.63
2.54
88
IIa
IIb
IIc
IId
IIe
IIf
C48H38Cl2N2O8
841.8
207 – 210
68.48
68.06
4.56
4.87
8.42
8.12
3.33
3.52
81
C49H40Cl2N2O8
855.8
185 – 188
68.76
68.21
4.72
4.99
8.28
7.87
3.27
3.56
62
C50H42Cl2N2O8
869.8
323 – 325
69.04
69.31
4.88
4.63
8.15
7.94
3.22
3.13
92
C52H42Cl2N2O8
897.9
295 – 297
69.55
69.83
5.17
4.98
7.90
7.65
3.12
3.21
35
C52H38Cl2N2O8
889.8
>360
95
70.18
69.94
4.31
4.12
7.97
8.11
3.15
3.02
C58H42Cl2N2O8
965.9
>360
90
72.12
71.97
4.39
4.48
7.34
7.12
2.90
3.01
IIg
IIh
IIIa
IIIb
IIIc
IIId
C59H44Cl2N2O8
980.0
218 – 220
72.31
72.74
4.53
4.57
7.24
7.07
2.86
2.98
85
C60H46Cl2N2O8
994.0
327 – 329
72.50
72.69
4.67
4.76
7.13
7.02
2.82
2.68
80
C18H26Cl2N2O8
469.4
295 – 297
46.06
45.79
5.59
5.83
15.11
14.81
5.97
5.90
81
C19H28Cl2N2O8
483.4
288 – 289
47.21
46.86
5.85
5.68
14.67
14.33
5.80
6.06
81
C20H30Cl2N2O8
497.4
266 – 268
48.29
48.53
6.09
5.91
14.25
14.16
5.63
5.75
51
C22H34Cl2N2O8
525.4
263 – 265
50.28
50.47
6.53
6.39
13.49
13.12
5.33
5.41
50
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TABLE I
(Continued)
Calculated/Found
Formula
M.w.
M.p., °C
Yield, %
Compound
% C
% H
% Cl
% N
IIIe
IIIf
C22H26Cl2N2O8
517.4
>380
83
51.07
51.36
5.08
4.91
13.70
13.42
5.42
5.66
C28H30Cl2N2O8
593.5
270 – 275
56.67
56.88
5.11
5.02
11.95
11.81
4.72
4.90
decomp.
85
IIIg
IIIh
IVa
IVb
IVc
Va
C29H32Cl2N2O8
607.5
275 – 277
57.33
57.60
5.32
5.21
11.67
11.46
4.61
4.54
90
C30H34Cl2N2O8
621.6
172 – 174
57.97
58.12
5.52
5.63
11.41
11.47
4.51
4.39
90
C19H18ClNO4
359.8
189 – 190
63.42
63.35
5.05
5.18
9.85
3.89
3.93
68
10.04
C21H22ClNO4
387.9
183 – 185
65.02
64.89
5.73
5.85
9.14
9.24
3.61
3.79
71
C25H22ClNO4
435.9
233 – 234
68.88
68.59
5.10
5.01
8.13
8.01
3.21
3.32
70
C14H16ClNO4
297.8
121
55
56.47
56.28
5.43
5.57
11.91
11.69
4.71
4.62
Vb
C16H20ClNO4
325.8
236 – 238
58.98
59.16
6.20
6.31
10.88
10.75
4.30
4.17
55
Vc
C20H20ClNO4
373.9
220 – 221
64.25
64.37
5.40
5.49
9.48
9.75
3.75
3.51
75
VIa
VIb
VIc
VId
VIIa
C9H14ClNO4
235.7
208 – 209
45.86
45.66
6.00
6.15
15.04
14.75
5.95
5.81
77
C11H18ClNO4
263.8
122
65
50.09
50.22
6.89
6.77
13.44
13.26
5.31
5.28
C15H18ClNO4
311.8
140
80
57.78
57.91
5.83
6.12
11.37
11.22
4.49
4.54
C11H18ClNO4
263.8
163 – 164
50.09
49.89
6.89
7.03
13.44
13.56
5.31
5.38
20
10.88
10.71
C16H20ClNO4
325.8
212 – 213
58.98
59.21
6.20
6.42
4.30
4.24
83
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New Compounds
2551
TABLE I
(Continued)
Calculated/Found
Formula
M.w.
M.p., °C
Yield, %
Compound
% C
% H
% Cl
% N
VIIb
VIIc
VIII
IX
C18H24ClNO4
353.9
185 – 186
61.09
60.87
6.85
6.99
10.02
9.86
3.96
3.84
64
C22H24ClNO4
401.9
151
76
65.74
65.29
6.03
6.18
8.82
8.74
3.49
3.38
C38H34Cl2N2O8
717.6
310 – 311.5
63.59
63.34
4.79
4.68
9.88
9.59
3.90
4.10
79
C33H32Cl2N2O8
655.6
348
74
60.46
60.31
4.93
4.87
10.82
10.69
4.27
4.16
X
C38H34Cl2N2O8
717.6
295 – 297
63.59
63.81
4.79
4.62
9.88
9.67
3.90
3.99
92
EXPERIMENTAL
The melting points were measured on a Boetius block. The NMR spectra were measured on Varian
1
XL-200 and Varian Unity-200 instruments (working frequency 200.057 MHz for H and 50.309 MHz
for 13C). The reported spectra (δ, ppm; J, Hz) were measured in (CD3)2SO. Hexamethyldisiloxane
(0.05 ppm) was used as the internal standard in 1H NMR spectroscopy, whereas the signals of the
solvents (39.7 ppm in (CD3)2SO; 77.0 ppm in CDCl3) served as reference in 13C NMR spectroscopy.
The numbering of the carbon atoms for the NMR signal assignment is given in the respective formulae.
The aliphatic chain in position 1 is numbered as usual; where it connects two pyridinium nuclei, the
numbering is from CH2-1 to CH2-3.
Synthesis of Compounds I, IV, V, VI, VII
2,4,6-Substituted pyrylium perchlorate (0.012 mol) was suspended in ethanol (18 ml) and the amine
(0.015 mol) was added. The suspension was stirred for 4 h at room temperature. The crystalline salt
was then filtered off, washed twice with ethanol and recrystallized from ethanol.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

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Synthesis of Compounds II, III, VIII, IX, X
The corresponding 2,4,6-substituted pyrylium perchlorate (0.008 mol) was suspended in ethanol (20 ml)
and the diamine (0.016 mol) was added. The suspension was stirred for 5 h at room temperature. The
deposited intermediate XI was sucked off, washed twice with ethanol and dried in air. To the product
so obtained was added an equimolar amount of the corresponding pyrylium perchlorate in ethanol
(20 ml) and the constantly stirred suspension was refluxed for 5 h. After cooling, the deposited sub-
stance was filtered off, washed twice with ethanol and dried in air. Physical characteristics of the
prepared compounds are given in Table I. Melting points of the compounds Ia – Id, Ig – Ii and VIe
are in accordance with the published data8,9. NMR spectra of the compounds I – X are given in
Tables II – XV.
TABLE II
13C NMR spectra of the compounds I
Position
Ia
Ib
Ic
Id
Ie
If
Ig
Ih
Ii
Ij
2, 6
3, 5
4
156.6 155.9 156.1 156.0 156.6 156.0 156.4 156.3 156.7 156.7
125.3 126.3 126.2 126.2 126.4 126.2 126.3 125.3 126.4 126.5
154.3 154.2 154.3 154.3 154.6 154.3 154.7 155.7 155.1 155.3
133.2 133.1 133.2 133.1 133.5 133.1 132.9 133.2 133.1 133.0
129.2 129.2 129.2 129.1 129.3 129.2 129.0 129.8 129.0 129.0
129.6 129.2 129.3 129.3 129.8 129.3 129.3 128.2 129.3 129.3
131.2 131.0 131.0 131.0 131.2 131.0 131.1 130.0 131.0 131.0
133.6 133.3 133.4 133.3 133.3 133.3 133.3 133.6 133.3 133.3
128.7 128.8 128.8 128.8 128.9 128.9 128.9 128.8 128.6 128.6
129.6 129.7 129.7 129.7 129.6 129.7 129.7 129.8 129.7 129.7
132.3 132.4 132.4 132.4 132.5 132.4 132.6 132.5 132.6 132.67
1′
2′, 6′
3′, 5′
4′
1′′
2′′, 6′′
3′′, 5′′
4′′
C1
45.8
–
50.3
56.0
22.6
10.5
–
54.1
30.8
18.8
12.5
–
61.2
28.8
19.3
–
54.4
56.7
–
–
–
–
–
57.9
57.3
C2
14.7
–
28.3 126.3
27.6 118.8
–
–
–
–
–
–
–
–
C3
–
C4
–
–
20.7
13.3
–
–
–
–
–
–
–
C5
–
–
–
–
1′′′
–
–
–
–
139.2 134.1 132.74
128.6 129.0 128.1
128.9 126.3 129.0
2′′′
–
–
–
–
–
–
–
–
3′′′
–
–
–
–
–
4′′′
–
–
–
–
–
–
128.1 133.1
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2553
TABLE III
1H NMR spectra of the compounds I
Compound
Arom.
2′′
3
The other positions
Ia
Ib
Ic
7.58 – 7.70 m, 9 H; 8.22 dd, 2 H,
7.85 m, 4 H
8.41 s, 2 H 3.77 s, 3 H (CH3)
4
3J = 10.3, J = 2.5
7.57 – 7.70 m, 9 H; 8.21 dd, 2 H,
8.41 s, 2 H 0.94 t, 3 H, J = 7.3 (CH3);
4.34 q, 2 H, J = 7.3 (CH2)
7.83 m, 4 H
7.57 – 7.71 m, 9 H; 8.21 dd, 2 H,
7.86 m, 4 H
3J = 8.9, 4J = 2.5
3J = 7.7, 4J = 2.5
8.41 s, 2 H 0.32 t, 3 H, J = 7.4 (CH3);
1.39 qt, 2 H, J = 7.4 (CH2-1);
4.28 t, 2 H, J = 7.4 (CH2-2)
Id
7.58 – 7.71 m, 9 H; 8.21 dd, 2 H,
7.86 m, 4 H
3J = 8.1, 4J = 2.0
8.42 s, 2 H 0.34 t, 3 H, J = 6.5 (CH3);
0.72 qt, 2 H, J = 6.5, 7.3(CH2-3);
1.36 tt, 2 H, J = 7.3, 7.6 (CH2-2);
4.31 t, 2 H, J = 7.6 (CH2-1)
Ie
If
7.64 – 7.71 m, 9 H; 8.29 dd, 2 H,
7.96 m, 4 H
3J = 8.0, 4J = 2.0
8.48 s, 2 H 0.38 d, 6 H, J = 6.8 (CH3);
1.51 septet of t, 1 H, J = 6.8, 7.3
(CH); 4.45 d, 2 H, J = 7.3 (CH2)
7.44 – 7.71 m, 8 H; 8.25 dd, 2 H,
8.46 s, 2 H 0.52 t, 3 H, J = 7 (CH3);
0.71 m, 4 H (CH2-3,4);
7.84 m, 4 H;
8.05 t, 1 H,
J = 7 (H-4′′)
3J = 8.0, 4J = 2.0
1.38 tt, 2 H, J = 8.0, 7.5 (CH2-2);
4.30 t, 2 H, J = 8.0 (CH2-1)
Ig
Ih
7.59 – 7.67 m, 9 H; 8.24 dd, 2 H,
7.77 m, 4 H
8.47 s, 2 H 4.57 d, 1 H, J = 17.5
(H-trans, =CH2);
3J = 8.2, 4J = 2.0
4.94 d, 2 H, J = 5.7 (CH2−N);
5.04 d, 1 H, J = 11.3
(H-cis, =CH2);
5.61 ddt, 1 H, J = 17.5, 11.3, 5.7
(−CH=)
7.14 m, 3 H;
7.33 m, 6 H;
7.45 m, 6 H;
7.64 m, 3 H
8.31 dd, 2 H,
8.62 s, 2 H
3J = 8.0, 4J = 2.5
Ii
Ij
7.53 – 7.73 m, 13 H 8.28 dd, 2 H,
3J = 8.1, 4J = 2.2
8.51 s, 2H 5.67 s, 2 H (CH2);
6.58 d, 2 H, J = 6.8 (H-2′′′, 6′′′);
7.10 m, 3 H (H-3′′′, 4′′′, 5′′′)
7.55 – 7.73 m, 13 H 8.28 dd, 2 H,
3J = 8.0, 4J = 0.8
8.52 s, 2 H 5.66 s, 2 H (CH2);
6.66 d, 2 H, J = 8.5 (H-3′′′, 5′′′);
7.10 d, 2 H, J = 8.5 (H-2′′′, 6′′′)
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

2554
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TABLE IV
13C NMR spectra of the compounds II
Position
IIa
IIb
IIc
IId
IIe
IIf
IIg
IIh
IIe (60 °C)
2,
.0 6151655.8
127.3
155.8
126.2
154.6
132.5
128.9
155.9
157.3
126.2
154.3
133.0
129.1
156.5
170.1
156.4
125.3
155.7
133.3
129.9
128.2
130.0
133.7
128.9
129.9
156.5
125.3
156.8
125.1
170.6
3, 5
4
126.1
125.7
115.6
127.4
115.2
156.0
154.4
132.7
129.0
155.6
165.9
155.8
165.3
155.6155.0
133.3
1′
132.0
133.9
129.5
133.3
129.2
133.3
129.7
127.8
129.8
133.5
128.6
129.4
2′, 6′
3′, 5′
4′
129.5
130.2
130.5
130.3
130.5
129.8
129.6129.3
129.2
129.2
128.7
129.2
130.5
128.3
130.5
131.8
132.9
129.2
129.9
133.2
131.1
133.1
128.8
129.7
131.2
133.2
128.8
129.7
131.0
133.3
128.8
129.7
130.4
130.3
130.4
130.0
1′′
134.0
129.0
133.7
132.6
133.7
2′′, 6′′
3′′, 5′′
4′′
129.1
129.2
128.8
129.4
129.0
130.2
128.7
129.3
129.8
132.6132.5
132.4
135.7
135.7
132.6132.6 134.8
132.9
C1
C2
C3
1′′′
2′′′
3′′′
4′′′
5′′′
6′′′
7′′′
8′′′
53.2
–
50.9
53.1
53.9
–
–
39.3
37.1
–
–
28.9
–
31.9
–
28.4
–
–
–
–
–
–
–
24.1
–
–
–
142.3
.3
–
–
–
–
148.2
129.7
114.1
133.0
–
141.4
126
142.2
128.8
129.8
137.2
–
148.8
–
–
–
–
128.3
112
–
–
–
–
125.8
140.5
138.8
123.0
121.4
138.5
129.0
137.3
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2555
TABLE V
1H NMR spectra of the compounds II
Compound
Arom.
2′′
3
The other positions
IIa
7.27 d, 8 H,
8.32 dd, 4 H,
8.27 s, 4 H 4.80 s, 4 H (CH2)
4
J = 7.2 (H-2′);
7.57 dd, 8 H,
J = 7.5 (H-3′);
7.73 m, 10 H
3J = 7.2, J = 1.6
IIb
IIc
IId
7.54 – 7.67 m, 26 H 8.16 d, 4 H, J = 7.8 8.26 s, 4 H 1.71 bs, 2 H (CH2-2);
3.77 bs, 4 H (CH2-1)
7.62 – 7.72 m, 26 H 8.24 d, 4 H, J = 6.8 8.40 s, 4 H 0.77 bs, 4 H (CH2-2);
3.82 bs, 4 H (CH2-1)
7.55 – 7.76 m, 26 H 8.20 d, 4 H, J = 8.7 8.39 s, 4 H 0.09 bs, 4 H (CH2-3);
1.05 bs, 4 H (CH2-2);
4.05 t, 4 H, J = 7.1 (CH2-1)
8.57 s, 2 H; 6.23 d, 2 H, J = 8.7 (H-2′′′);
9.17 s, 2 H 6.97 d, 2 H, J = 8.7 (H-3′′′)
IIe
7.41 m, 11 H;
7.65 m, 4 H;
7.83 m, 9 H
8.32 dd, 2 H,
4
3J = 8.0, J = 2.0;
8.48 d, 2 H, J = 8.0
IIf
7.33 – 7.83 m, 30 H; 8.31 dd, 2 H,
8.57 m, 6 H
8.59 s, 2 H;
9.09 s, 2 H
4
3J = 8.0, J = 2.0
IIg
IIh
7.30 – 7.44 m, 24 H; 8.32 d, 4 H, J = 8.3 8.64 s, 4 H 3.63 s, 2 H (CH2);
7.66 m, 6 H
7.42 m, 20 H;
7.67 m, 6 H
6.57 d, 4 H, J = 8.5 (H-3′′′)
8.63 s, 4 H 2.43 s, 4 H (CH2);
6.30 d, 4 H, J = 8.0 (H-3′′′);
8.33 dd, 4 H,
4
3J = 8.3, J = 3.0
7.23 d, 4 H, J = 8.0 (H-2′′′)
IIe (60 °C) 7.31 s, 6 H;
8.24 dd, 4 H,
8.39 s, 4 H 7.28 s, 4 H (H-2′′′, 3′′′)
4
7.42 – 7.68 m, 20 H 3J = 7.9, J = 2.0
TABLE VI
13C NMR spectra of the compounds III
Position
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IIIh
2, 6
3, 5
4
CH3-2
CH3-4
CH2-1
CH2-2
CH2-3
1′
155.4
129.0
159.1
21.1
21.15
49.2
–
–
–
–
–
154.7
128.3
157.6
20.8
21.0
48.6
25.6
–
–
–
–
–
154.4
128.3
157.3
20.6
21.0
51.2
24.7
–
–
–
–
–
154.2
128.3
157.1
20.4
20.9
51.8
27.4
25.5
–
154.8
129.0
159.7
21.7
21.5
–
155.0
129.0
159.4
21.8
21.6
–
154.9
127.3
159.1
21.7
21.4
40.0
–
154.9
127.3
159.1
21.6
21.4
36.3
–
–
–
–
–
–
–
140.0
127.4
–
140.8
127.0
127.5
138.6
143.5
126.2
131.2
136.8
144.3
125.7
131.0
136.5
2′
3′
4′
–
–
–
–
–
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

2556
Urban, Volke:
TABLE VII
1H NMR spectra of the compounds III
Compound
3, 5
CH3-2
CH3-4
The other positions
IIIa
IIIb
7.82 s, 4 H
7.72 s, 4 H
2.77 s, 12 H
2.83 s, 12 H
2.52 s, 6 H
2.47 s, 6 H
5.04 s, 4 H (2 × CH2-1)
2.33 m, 2 H (CH2-2);
4.67 t, 4 H, J = 8.0 (2 × CH2-1)
IIIc
IIId
7.73 s, 4 H
7.72 s, 4 H
2.82 s, 12 H
2.79 s, 12 H
2.48 s, 6 H
2.47 s, 6 H
1.96 bs, 4 H (2 × CH2-2);
4.45 bs, 4 H (2 × CH2-1)
1.54 bs, 4 H (2 × CH2-3);
1.80 bs, 4 H (2 × CH2-2);
4.39 bs, 4 H (2 × CH2-1)
IIIe
IIIf
7.96 s, 4 H
7.95 s, 4 H
2.38 s, 12 H
2.38 s, 12 H
2.62 s, 6 H
2.63 s, 6 H
7.99 s, 4 H (H-2′,3′,5′,6′)
7.78 d, 4 H, J = 6.4 (H-3′,5′);
8.19 d, 4 H, J = 6.4 (H-2′,6′)
IIIg
IIIh
7.89 s, 4 H
7.89 s, 4 H
2.29 s, 12 H
2.27 s, 12 H
2.58 s, 6 H
2.59 s, 6 H
4.27 s, 2 H (CH2);
7.56 and 7.64 ABq, 8 H, J = 8.1
(H-2′,3′,5′,6′)
3.11 s, 4 H (2 × CH2) ;
7.46 and 7.50 ABq, 8 H, J = 8.6
(H-2′,3′,5′,6′)
TABLE VIII
1H NMR spectra of the compounds V
Position
Va
Vb
Vc
3, 5
8.20 s, 2 H
8.26 s, 2 H
7.99 dd, 2 H,
8.42 s, 2 H
2′, 6′
7.94 dd, 2 H,
8.09 dd, 2 H,
4
4
3J = 8.0, J = 2.5 3J = 8.0, J = 2.8
3J = 6.5, 4J = 3.4
3′, 4′, 5′
7.58 m, 3 H
2.77 s, 6 H
7.63 m, 3 H
2.89 s, 6 H
7.66 m, 3 H
2.79 s, 6 H
CH3 (2, 6)
The other positions 3.97 s, 3 H (CH3) 1.05 t, 3 H, J = 7.1 (CH3);
5.89 s, 2 H (CH2);
7.10 dd, 2 H, 3J = 7.8,
4J = 1.9 (H-2′′, 6′′);
1.84 qt, 2 H, J = 7.1, 8.6
(CH2-2);
4.40 t, 2 H, J = 8.6 (CH2-1) 7.40 m, 3 H (H-3′′, 4′′, 5′′)
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2557
TABLE IX
13C NMR spectra of the compounds IV and V
Position
IVa
IVb
IVc
Va
Vb
Vc
2
156.0
124.0
153.5
124.8
156.8
133.2
129.2
129.3
131.0
133.6
128.3
129.7
132.1
21.5
42.3
–
155.8
124.8
153.6
125.8
155.9
133.2
129.1
129.1
130.8
133.5
128.3
129.7
132.2
21.0
54.5
22.2
10.8
–
156.4
125.1
154.5
126.2
156.5
133.4
128.9
128.5
130.9
133.6
128.5
129.7
132.4
21.4
155.9
155.4
124.3
153.3
–
156.1
124.7
154.2
–
3
123.5
4
153.1
5
–
6
–
–
–
1′
133.7
133.6
127.9
129.7
131.9
–
133.6
128.2
129.8
132.2
–
2′, 6′
3′, 5′
4′
127.9
129.7
131.9
1′′
–
–
2′′, 6′′
3′′, 5′′
4′′
–
–
–
–
–
–
–
–
CH3-2 (6)
C1
21.5
39.8
–
20.7
53.4
21.3
11.0
–
21.1
54.9
–
56.3
C2
–
C3
–
–
–
–
1′′′(1′′)
2′′′(2′′)
3′′′(3′′)
4′′′(4′′)
–
132.9
125.8
129.2
128.3
–
132.7
125.7
129.5
128.4
–
–
–
–
–
–
–
–
–
–
–
–
TABLE X
1H NMR spectra of the compounds VI
Compound
3
CH3-2, 6
CH3-4
The other positions
3.96 s, 3 H (CH3)
VIa
VIb
7.68 s, 2 H
7.71 s, 2 H
2.71 s, 6 H
2.79 s, 6 H
2.46 s, 3 H
2.46 s, 3 H
1.01 t, 3 H, J = 6.7 (CH3);
1.78 qt, 2 H, J = 6.7, 8.8 (CH2-2);
4.35 t, 2 H, J = 8.8 (CH2-1)
VIc
7.83 s, 2 H
2.68 s, 6 H
2.54 s, 3 H
5.83 s, 2 H (CH2);
7.01 d, 2 H, J = 7.9 (H-2′, 6′);
7.37 m, 3 H (H-3′, 4′ 5′)
VId
VIe
7.69 s, 2 H
7.66 s, 2 H
2.82 s, 6 H
2.70 s, 6 H
2.45 s, 3 H
2.45 s, 3 H
1.65 d, 6 H, J = 7.2 (2 × CH3);
5.35 septet, 1 H, J = 7.2 (CH)
6.87 bs, 2 H (NH2)
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

2558
Urban, Volke:
TABLE XI
13C NMR spectra of the compounds VI and VII
Position
VIa
VIb
VIc
VId
VIe
VIIa
VIIb
VIIc
2, 6
154.9
154.2
128.3
157.1
–
154.9
128.6
158.4
–
154.7
153.8
160.3
122.1
153.8
134.1
128.1
129.7
131.8
27.1
12.1
–
159.8
122.7
153.9
134.0
128.2
129.6
131.8
26.3
13.2
–
160.5
123.1
154.8
134.0
128.4
129.7
132.1
26.8
12.9
–
3, 5
127.5
128.7
127.4
4
156.9
156.8
154.6
1′
–
–
–
–
–
–
2′, 6′
3′, 5′
4′
–
–
–
–
–
–
–
–
–
–
–
–
CH2-2
CH3-2(6)
CH3-4
C1
–
–
–
–
–
21.2
21.0
39.7
–
20.4
20.8
53.2
21.3
10.8
–
20.8
21.2
54.8
–
20.2
20.6
57.9
22.1
–
19.8
20.9
–
38.7
–
52.1
23.0
10.8
–
53.8
–
C2
–
C3
–
–
–
–
–
1′ (1′′)
2′ (2′′)
3′ (3′′)
4′ (4′′)
–
132.7
125.6
129.5
128.3
–
–
–
133.8
125.6
129.4
128.3
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
TABLE XII
1H NMR spectra of the compounds IV
Position
IVa
IVb
IVc
3
8.22 bs, 1 H
8.49 bs, 1 H
8.11 dd, 2 H,
8.20 d, 1 H, J = 2.5
8.51 d, 1 H, J = 2.5
8.33 s, 1 H
8.60 s, 1 H
5
2′′, 6′′
8.11 dd, 2 H,
8.18 dd, 2 H,
4
3J = 9.0, 4J = 2.4 3J = 9.4, J = 2.0
3J = 8.0, 4J = 2.0
Arom.
7.59 – 7.68 m, 8 H 7.59 – 7.68 m, 8 H
7.60 m, 8 H
2.82 s, 3 H
CH3 (2)
2.91 s, 3 H
2.99 s, 3 H
The other positions 3.92 s, 3 H (CH3) 0.68 t, 3 H, J = 7.1 (CH3);
5.73 s, 2 H (CH2);
1.68 qt, 2 H, J = 7.1
(CH2-2);
7.01 d, 2 H, J = 8.0 (H-2′′′);
7.31 m, 3 H (H-3′′′, 4′′′, 5′′′)
4.27 t, 2 H, J = 8.0
(CH2-1)
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2559
TABLE XIII
13C NMR spectra of the compounds VIII – X
Position
VIII
IX
X
2, 6
156.5
127.0
155.5
155.7
124.3
154.2
132.7
129.76
129.79
131.7
133.1
129.1
130.3
132.9
133.3
128.0
129.9
132.3
19.1
–
156.5
127.0
155.5
154.5
128.3
158.3
132.6
129.8
130.3
131.7
133.1
129.0
129.8
132.9
–
156.16, 156.2
3, 5
123.5
4
155.1, 155.2
2′, 6′
3′, 5′
4′
128.4
128.3
130.0
1a
–
2a, 6a
3a, 5a
4a
–
–
–
1b
–
2b, 6b
3b, 5b
4b
–
–
–
1′a
–
2′a, 6′a
3′a, 5′a
4′a
–
–
–
–
–
–
CH3-2′, 6′
CH3-4′
CH2(1)
CH2(2)
1′
18.8
20.9
49.7
48.3
–
–
–
–
49.8
48.5
–
–
133.9
1′′
–
–
140.8, 142.0
120.8
2′′, 6′′
3′′, 5′′
4′′
–
–
–
–
126.6
–
–
137.5, 138.6
22.1
CH3-2, 6
–
–
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

2560
Urban, Volke:
TABLE XIV
1H NMR spectra of the compounds VIII – X
Position
VIII
IX
X
3, 5
8.53 s, 2 H
8.05 s, 2 H
8.52 s, 2 H
7.48 s, 2 H
8.59 s, 2 H; 8.62 s, 2 H
3′, 5′
8.28 dd, 2 H,
2b, 6b
8.30 d, 2 H, J = 7.3
7.91 d, 2 H, J = 7
4
3J = 7.3, J = 1.6
2′a, 6′a
2′′, 6′′
3′′, 5′′
7.25 d, 2 H, J = 8.5
7.86 d, 2 H, J = 8.5
7.61 m, 7 H; 7.79 m, 5 H; 7.64 m, 3 H; 7.77 m, 6 H; 7.77 m, 8 H;
Ar−H
8.05 s, 6 H
8.00 m, 4 H
8.06 – 8.34 m, 6 H
CH2 (1)
CH2 (2)
CH3-2′, 6′
CH3-4
4.37 t, 2 H, J = 8.6
5.11 t, 2 H, J = 8.6
1.78 s, 6 H
4.33 t, 2 H, J = 8.5
5.04 t, 2 H, J = 8.5
1.66 s, 6 H
2.46 s, 6 Ha; 2.49 s, 6 Ha
2.34 s, 3 H
a
CH3-2, 6.
TABLE XV
1H NMR spectra of the compounds VII
Position
VIIa
VIIb
VIIc
3
8.15 s, 2 H
8.15 s, 2 H
8.30 s, 2 H
2′
8.07 dd, 2 H,
8.07 dd, 2 H,
8.15 dd, 2 H,
4
3J = 7.5, 4J = 2.1 3J = 7.4, J = 2.4
3J = 7.2, 4J = 2.5
3′, 4′, 5′
CH3-2
CH2-2
7.63 m, 3 H
7.62 m, 3 H
7.66 m, 3 H
1.38 t, 6 H, J = 7.1 1.43 t, 6 H, J = 7.7
1.33 t, 6 H, J = 7.2
3.09 q, 4 H, J = 7.2
3.17 q, 4 H,
3.19 q, 4 H, J = 7.7
J = 7.1
The other positions 4.11 s, 3 H (CH3) 1.07 t, 3 H, J = 6.8 (CH3);
5.93 s, 2 H (CH2);
1.84 qt, J = 6.8, 8.3 (CH2-2); 7.09 d, 2 H, J = 7.3
4.42 t, 2 H, J = 8.3 (CH2-1) (H-2′′, 6′′);
7.39 m, 3 H (H-3′′, 4′′, 5′′)
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
2561
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3. Urban J.: Ph.D. Thesis. The J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences
of the Czech Republic, Prague 1992.
4. Wizinger R., Losinger S., Ulrich P.: Helv. Chim. Acta 39, 5 (1956).
5. Balaban A. T., Nenitzescu C. D.: Ann. Chem. 625, 74 (1959).
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7. Diels O., Alder K.: Chem. Ber. 60, 716 (1927).
8. Katritzky A. R., Bapat J. B., Blade K. J., Leddy B. P., Nie P. L., Ramsden C. A., Thind S. S.: J.
Chem. Soc., Perkin Trans. 1 1979, 418.
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Translation revised by P. Adamek.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)