11-Aryl-3,3-dimethyl-7- and 7,8-substituted 1,2,3,4,10,11-hexahydro-5H- dibenzo[b,e]-1,4-diazepin-1-ones

Article abstract of DOI:10.1023/B:COHC.0000044581.23486.59

In reactions of 3-(5- and 5,6-substituted 2-aminophenylamino)-5,5- dimethylcyclohex-2-en-ones with carbaldehydes of pyridine, thiophene, and furan and substituted benzaldehydes, we have obtained 21 novel 7H-7-methoxycarbonyl-, 7-benzoyl-, 7-trifluoromethy

Full text of DOI:10.1023/B:COHC.0000044581.23486.59

Chemistry of Heterocyclic Compounds, Vol. 40, No. 7, 2004
11-ARYL-3,3-DIMETHYL-7- AND
7,8-SUBSTITUTED 1,2,3,4,10,11-HEXAHYDRO-
5H-DIBENZO[b,e]-1,4-DIAZEPIN-1-ONES
N. N. Tonkikh, A. Strakovs, K. V. Rizhanova, and M. V. Petrova
In reactions of 3-(5- and 5,6-substituted 2-aminophenylamino)-5,5-dimethylcyclohex-2-en-ones with
carbaldehydes of pyridine, thiophene, and furan and substituted benzaldehydes, we have obtained
21 novel 7H-7-methoxycarbonyl-, 7-benzoyl-, 7-trifluoromethyl-, 7-nitro- and 7,8-dichloro-11-aryl-3,3-
dimethyl-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e]-1,4-diazepin-1-one.
Keywords: dimedone, substituted 1,2-phenylenediamines, pyridine-, thiophene-, furancarbaldehydes,
dibenzo[b,e]-1,4-diazepine derivatives.
Modification of dibenzo[b,e]-1,4-diazepines is part of extensive research on synthesis of derivatives of
tricyclic systems including a 1,4-diazepine moiety, among which pyrido[2,3-b]benzo[e]-1,4-diazepines and
dipyrido[3,2-b:2,3-e]-1,4-diazepines are key derivatives according to the criterion of pharmacological value
[1-11].
In an extension of [12], in this study we obtained dibenzo[e]-1,4-diazepines by the method used in
[13-16]: reaction of 3-(2-aminophenylamino)-5,5-dimethylcyclohex-2-en-1-ones with pyridine-, thiophene-,
furancarbaldehydes and substituted benzaldehydes.
By boiling 1,2-phenylenediamines 1a-f with dimedone 2 in toluene in the presence of catalytic amounts
of p-toluenesulfonic acid under conditions for azeotropic distillation of water, we obtained
(2-aminophenyl)aminocyclohexenes 3a-f. When using 5-substituted 1,2-phenylenediamines 1b-e, two isomeric
1
enaminones could be formed. In the H NMR spectra of the latter, we observe a broadened two-proton signal
from the primary amino group in the 3.76-5.81 ppm region, one six-proton singlet from the methyl groups and
two two-proton singlets from the CH2 groups of the dimedone moiety. The proton at the C(2) atom absorbs in the
interval 4.65-5.07 ppm, while the enamine NH proton absorbs downfield at 7.56-8.23 ppm. The spatial
proximity of the enamine NH and aromatic C(6)–H protons is proven based on 1H NMR difference spectroscopy
(NOE), which made it possible to choose in favor of the structures 3b-e.
The reaction of enamines 3a-f with substituted benzaldehydes, 2-, 3-, 4-pyridinecarbaldehydes,
2-thiophenecarbaldehyde (4a-j) was carried out by boiling in ethanol in the presence of catalytic amounts of
H2SO4, while the reaction with furfural 4k was carried out in the presence of piperidine acetate.
1
The structure of the dibenzodiazepines in 5a-u was confirmed by IR and H NMR spectra. In the
1H NMR spectra, the methyl groups of the dimedone moiety are magnetically nonequivalent, and are detected as
two three-proton singlets in the 0.98-1.05 ppm range. The protons from one of the methylene groups are also
magnetically nonequivalent in some diazepines 5, and their absorption is represented by an AB spin system with
geminal constant 16-18 Hz.
__________________________________________________________________________________________
Riga Technical University, Riga LV-1048, Latvia; e-mail: marina@osi.lv. Translated from Khimiya
Geterotsiklicheskikh Soedinenii, No. 7, pp. 1101-1107, July, 2004. Original article submitted March 19, 2002;
revision submitted September 29, 2003.
0009-3122/04/4007-0949©2004 Springer Science+Business Media, Inc.
949

H
N
R
NH2
NH2
HO
R
+
R'
R'
NH2
1a–f
O
O
3a–f
2
ArCHO
4a–k
H
R
N
R'
N
O
Ar
H
5a–u
1, 3 a R = R' = H; b R = COOMe, R' = H; c R = COPh, R' = H; d R = CF3, R' = H; e R = NO2, R' = H; f R = R' = Cl;
4 a Ar = C6H3F2-3,5; b Ar = C6H3O2CH2-3,4; c Ar = C6H4NO2-3; d Ar = C6H4Cl-4; e Ar = C6H4F-4;
f Ar = C6H3(OMe)2-3,4; g Ar = 2-pyridyl, h Ar = 3-pyridyl, i Ar = 4-pyridyl, j Ar = 2-thienyl, k Ar = 2-furyl;
5 a-r R' = H, s-u R' = Cl; a R = H, Ar = C6H3F2-3,5; b R = H, Ar = 2-pyridyl; c R = Н, Ar = 3-pyridyl;
d R = Н, Ar = 4-pyridyl; e R = COOMe, Ar = C6H3O2CH2-3,4; f R = COOMe, Ar = C6H3F2-3,5; g R = COOMe, Ar = 3-pyridyl;
h R = COOMe, Ar = 4-pyridyl; i R = COPh, Ar = C6H4NO2-3; j R = COPh, Ar = 4-pyridyl; k R = COPh, Ar = 2-thienyl;
l R = COPh, Ar = 2-furyl; m R = CF3, Ar = C6H4Cl-4; n R = CF3, Ar = C6H4F-4; o R = CF3, Ar = 2-thienyl;
p R = CF3, Ar = 2-furyl; q R = NO2, Ar = 2-thienyl; r R = NO2, Ar = 2-furyl; s R = Cl,
Ar = C6H3(OMe)2-3,4; t R = Cl, Ar = C6H3F2-3,5; u R = Cl, Ar = 4-pyridyl
The signals from the protons at the tertiary C(11) atom are detected as doublets in the interval
δ 5.68-6.82 ppm with vicinal spin–spin coupling constant 5 Hz. The N(10)–H proton is represented by such a
doublet (δ 6.58-5.53) in most of the diazepines 5, except in cases when it is overlapped by aromatic signals. The
N(5)–H signals resonate downfield: δ 8.93-9.12 ppm.
EXPERIMENTAL
The IR spectra were recorded on a Specord IR-75 for suspensions of the compounds in vaseline oil
(1800-1500 cm-1 region) and in hexachlorobutadiene (3600-2000 cm-1 region). In the 1800-1500 cm-1 region,
only the carbonyl frequencies are given. The frequencies of the stretching vibrations of the C–H bond in the
1
3050-2800 cm-1 region are not given. The H NMR spectra were recorded on a Bruker WH/90DS (90 MHz),
internal standard TMS.
In this work, we used diamines and aldehydes from Lancaster, Acros, and Fluka.
To monitor the course of the reactions, we used Merck Silica Gel 60 F254 plates, with the systems 7:3
ethyl acetate–toluene (A), 4:3 ethyl acetate–toluene (B); visualization by heating and exposure to UV light.
3-(2-Aminophenylamino)-5,5-dimethylcyclohex-2-en-1-one (3a) was obtained by the procedure in
[13].
3-(2-Amino-5-methoxycarbonylphenylamino)- (3b), 3-(2-Amino-5-benzoylphenylamino)- (3c), 3-(2-
Amino-5-trifluoromethylphenylamino)- (3d), 3-(2-Amino-5-nitrophenylamino)- (3e), 3-(2-Amino-4,5-
dichlorophenylamino)- (3f) 5,5-dimethylcyclohex-2-en-1-ones. Dimedone 2 (5 mmol) and the corresponding
diamine 1b-f (5 mmol) were boiled in toluene (100 ml) in the presence of catalytic amounts of p-toluenesulfonic
acid under conditions for azeotropic distillation of water for 3 h. The enamine 3e that precipitated upon cooling
950

TABLE 1. Characteristics of Synthesized Compounds
Found, %
Calculated, %
——————
Com-
pound
Empirical
formula
mp, °С
Yield, %
С
Н
N
Сl (S)
3b
3c
3d
3e
3f
C16H20N2O3
66.65
66.65
75.25
75.42
60.50
60.39
60.89
61.08
56.16
56.20
71.02
71.17
75.01
75.20
75.14
75.20
75.05
75.20
68.73
68.56
67.11
66.98
70.17
70.01
69.84
70.01
71.79
71.93
76.66
76.57
72.67
72.87
75.80
75.71
62.61
62.78
65.15
65.34
61.11
61.21
63.65
63.82
61.60
61.77
64.43
64.58
61.54
61.75
6.77
6.99
6.60
6.63
5.71
5.75
6.15
6.23
5.50
5.39
5.60
5.69
6.48
6.63
6.60
6.63
6.66
6.63
5.70
5.75
5.30
5.38
6.09
6.14
6.02
6.14
5.30
5.39
5.82
5.95
5.60
5.65
5.81
5.86
4.80
4.79
4.91
4.99
4.97
4.88
5.01
5.09
5.13
5.18
5.30
5.42
5.32
5.41
9.84
9.72
8.31
8.38
9.18
9.39
15.11
15.26
9.29
9.36
7.79
7.90
13.13
13.16
13.97
13.16
13.11
13.16
6.52
6.66
6.68
6.79
11.10
11.13
11.18
11.13
8.79
8.99
10.01
9.92
6.43
6.54
6.65
6.79
6.55
6.66
6.81
6.93
7.00
7.14
7.28
7.44
11.21
11.37
11.70
11.89
6.12
6.26
213-214
145-146
211-211
204-206
218-219
247-248
230-233
216-218
260-263
235-236
181-182
261-263
280-281
263-265
266-269
284-285
269-271
220-222
206-207
258-260
269-271
289-290
278-280
188-189
149-151
266-268
35
66
81
55
54
46
53
94
88
36
60
54
53
87
51
42
87
86
74
80
78
68
77
45
83
51
C21H22N2O2
C15H17F3N2O
C14H17N3O3
C14H16Cl2N2O
C21H20F2N2O
C20H21N3O
23.50
23.70
5a
5b
5c
5d
5e
5f
C20H21N3O
C20H21N3O
C24H24N2O5
C23H22F2N2O3
C22H23N3O3
C22H23N3O3
C28H25N3O4
C27H25N3O2
C26H24N2O2S
C26H24N2O3
C22H20 ClF3N2O
C22H20F4N2O
C20H19F3N2OS
C20H19F3N2O2
C19H19N3O3S
C19H19N3O4
C23H24Cl2N2O3
C21H18Cl2F2N2O
C20H19Cl2N3O
5g
5h
5i
5j
5k
5l
(7.30)
(7.48)
5m
5n
5o
5p
5q
5r
5s
5t
(8.40)
(8.17)
(8.70)
(8.68)
15.60
15.85
16.60
16.75
18.10
18.26
59.40
59.59
61.66
61.86
4.25
4.29
4.90
4.93
6.49
6.62
10.75
10.82
5u
was recrystallized from toluene. In the rest of the cases, the toluene was completely driven off on a rotary
evaporator, the dry residue (with addition of activated carbon) was recrystallized from THF (compounds 3c,d),
toluene (compound 3b), or ethanol (compound 3f).
951

TABLE 2. Spectral Characteristics of Synthesized Compounds
IR spectrum
Com-
pound
1Н NMR spectrum (DMSO-d6), δ, ppm (SSCC, J, Hz)
ν, cm-1
1
2
3
3b
1706, 1630;
3460, 3330,
3220
1.03 (6Н, s, 2СН3); 2.03 (2Н, s, СН2); 2.43 (2Н, s, СН2);
3.78 (3Н, s, OСН3); 4.65 (1Н, d, =СН); 5.81 (2H, br. s, NH2);
6.74 (1H, d, 3J = 8, C6H3); 7.44 (1H, d, 4J = 2, C6H3);
7.56 (1Н, dd, 3J = 8, 4J = 2, C6H3); 8.09 (1H, br. s, NH)
3с
1645, 1625;
3480, 3280,
3200
0.95 (6Н, s, 2СН3); 1.96 (2Н, s, СН2); 2.33 (2Н, s, СН2);
4.62 (1Н, s, =СН); 5.93 (2H, br. s, NH2); 6.77 (1H, d, 3J = 8, C6H3);
7.36-7.64 (7H, m, С6Н5, C6H3); 8.16 (1H, br. s, NH)
3d
1630; 3450,
3300, 3180
0.97 (6Н, s, 2СН3); 1.96 (2Н, s, СН2); 2.33 (2Н, s, СН2);
4.56 (1Н, s, =СН); 5.58 (2H, br. s, NH2); 6.82 (1H, d, 3J = 8, C6H3);
7.11 (1H, d, 4J = 2, С6Н3); 7.29 (1H, dd, 3J = 8, 4J = 2, С6Н3);
8.17 (1H, br. s, NH)
3е
1635;
3480, 3340,
3240
1.01 (6Н, s, 2СН3); 2.02 (2Н, s, СН2); 2.41 (2Н, s, СН2);
4.61 (1Н, s, =СН); 6.41 (2H, br. s, NH2); 6.82 (1H, d, 3J = 8, C6H3);
7.81 (1H, d, 4J = 2, С6Н3); 7.91 (1H, dd, 3J = 8, 4J = 2, С6Н3);
8.24 (1H, br. s, NH)
3f
1635;
3400, 3300,
3220
1.01 (6Н, s, 2СН3); 2.16 (2Н, s, СН2); 2.36 (2Н, s, СН2);
3.76 (2Н, br. s, NH2); 5.07 (1Н, s, =СН); 6.92 (1H, s, C6H2);
7.14 (1H, s, С6Н2); 7.56 (1H, br. s, NH)
5а
5b
1630;
3300, 3220,
3100
1633;
3300, 3200,
3100
0.98 (3Н, s, СН3); 1.07 (3Н, s, СН3); 2.11 (2Н, s, СН2);
2.56 (2Н, s, СН2); 5.93 (1Н, s, СН); 6.16 (1H, br. s, NH);
6.53-6.97 (7Н, m, С6Н4, C6H3); 8.78 (1H, br. s, NH)
0.93 (3Н, s, СН3); 0.98 (3Н, s, СН3); 1.96 (1Н, d, 2J = 16, СН);
2.13 (1Н, d, 2J = 16, СН); 2.51 (2Н, s, СН2); 5.73 (1Н, d, 3J = 5, СН);
6.04 (1Н, d, 3J = 5, NН); 6.53-7.02 (6Н, m, С6Н4, C5H4N);
7.41 (1H, m, С5H4N); 8.33 (1H, m, С5H4N); 8.71 (1H, br. s, NH)
5c
1628;
1.01 (3Н, s, СН3); 1.08 (3Н, s, СН3); 2.12 (1Н, d, 2J = 18, СН);
33320, 3210, 2.26 (1Н, d, 2J = 18, СН); 2.61 (2Н, s, СН2); 5.76 (1Н, d, 3J = 5, СН);
100
6.26 (1Н, d, 3J = 5, NН); 6.56-7.47 (6Н, m, С6Н4, C5H3N);
8.21 (1H, dd, 3J = 5, 4J = 1.5, С5H4N); 8.37 (1H, d, 4J = 1.5, С5H4N);
8.92 (1H, br. s, NH)
5d
1630; 3300,
3190, 3100
0.95 (3Н, s, СН3); 1.03 (3Н, s, СН3); 2.07 (1Н, d, 2J = 16, СН);
2.19 (1Н, d, 2J = 16, СН); 2.58 (2H, s, CH2); 5.64 (1Н, d, 3J = 5, СН);
6.27 (1Н, d, 3J = 5, NН); 6.47-6.98 (6Н, m, С6Н4, C5H4N);
8.27 (2H, m, С5H4N); 8.78 (1H, br. s, NH)
5е
1710, 1630;
3320, 3180,
3080
1.01 (3Н, s, СН3); 1.12 (3Н, s, СН3); 2.12 (1Н, d, 2J = 17, СН);
2.23 (1Н, d, 2J = 17, СН); 2.65 (2Н, m, СН2); 3.81 (3Н, s, OСН3);
5.67 (1Н, d, 3J = 5, СН); 5.92 (2Н, s, О-СН2-О);
6.56 (4Н, m, 2С6Н3); 6.92 (1H, d, 3J = 5, NН);
7.24 (1Н, dd, 3J = 8, 4J = 2, C6H3); 7.74 (1Н, d, 3J = 2, C6H3);
9.05 (1H, br. s, NH)
5f
1710, 1635;
3300, 3200
1.01 (3Н, s, СН3); 1.11 (3Н, s, СН3); 2.18 (2Н, s, СН2);
2.63 (2Н, s, СН2); 3.78 (3Н, s, OСН3); 5.76 (1Н, d, 3J = 5, СН);
6.47 (1H, d, 3J = 5, NH); 6.66-7.02 (4H, m, 2С6Н3);
7.34 (1H, dd, 3J = 8, 4J = 1.5, С6Н3); 7.69 (1Н, d, 4J = 1.5, C6H3);
9.09 (1H, br. s, NH)
5g
1705,1638;
3330,
3100-3050
0.99 (3Н, s, СН3); 1.07 (3Н, s, СН3); 2.02 (1Н, d, 2J = 18, СН);
2.18 (1Н, d, 2J = 18, СН); 2.59 (2Н, s, СН2); 3.78 (3Н, s, OСН3);
5.83 (1Н, d, 3J = 5, СН); 6.65 (1H, d, 3J = 8, C6H3);
6.96 (1H, d, 3J = 5, NH); 7.03-7.53 (3Н, m, C5H4N, C6H3);
7.77 (1Н, d, 4J = 2, C6H3); 8.26-8.41 (2Н, m, C5H4N);
9.12 (1H, br. s, NH)
5h
1706, 1640;
3300, 3080
1.01 (3Н, s, СН3); 1.12 (3Н, s, СН3); 2.14 (1Н, d, 2J = 16, СН);
2.21 (1Н, d, 2J = 16, СН); 2.55 (2Н, m, СН2); 3.76 (3Н, s, OСН3);
5.76 (1Н, d, 3J = 5, СН); 6.68 (1H, d, 3J = 8, C6H3);
6.96 (3H, m, 3J = 5, C5H4N, NH); 7.32 (1H, dd, 3J = 8, 4J = 2, C6H3);
7.41 (1H, d, 4J = 2, C6H3); 8.41 (2Н, m, 3J = 5, C5H4N);
9.12 (1H, br. s, NH)
952

TABLE 2 (continued)
1
2
3
5i
1640, 1630;
3350, 3200,
3080
0.94 (3Н, s, СН3); 1.08 (3Н, s, СН3); 2.07 (1Н, d, 2J = 18, СН);
2.18 (1Н, d, 2J = 18, СН); 2.61 (2Н, s, СН2); 5.88 (1Н, d, 3J = 5, СН);
6.72 (1H, d, 3J = 8, C6H3); 7.18 (3H, m, С6H3, NH);
7.57 (6Н, m, C6H5, C6H4); 7.97-8.07 (3Н, m, C6H4);
9.08 (1H, br. s, NH)
5j
5k
5l
1645, 1630;
3320, 3180,
3070
0.99 (3Н, s, СН3); 1.02 (3Н, s, СН3); 2.03 (1Н, d, 2J = 16, СН);
2.15 (1Н, d, 2J = 16, СН); 2.53 (2Н, s, СН2); 5.71 (1Н, br. s, СН);
6.66 (1H, d, 3J = 8, C6H3); 7.07-7.56 (9Н, m, C5H4N, C6H4, NH);
8.31 (3Н, m, C6H4, C6H3); 8.98 (1H, br. s, NH)
1.01 (3Н, s, СН3); 1.03 (3Н, s, СН3); 2.06 (1Н, d, 2J = 17, СН);
2.18 (1Н, d, 2J = 17, СН); 2.53 (2Н, s, СН2); 5.96 (1Н, d, 3J = 2, СН);
6.74-7.08 (5Н, m, C6H3, C4H3S); 7.04 (1H, d, 3J = 5, NH);
7.59 (6Н, m, C6H5, C6H3); 8.99 (1H, br. s, NH)
0.93 (3Н, s, СН3); 1.03 (3Н, s, СН3); 2.11 (1Н, d, 2J = 17, СН);
2.26 (1Н, d, 2J = 17, СН); 2.53 (2Н, s, СН2); 5.77 (3Н, m, C4H3O);
6.14 (1Н, m, C6H3); 6.71 (1Н, d, 3J = 5, СН); 7.08 (2H, m, C6H3, NH);
7.36-7.69 (6Н, m, C6H5, C6H3); 8.98 (1H, br. s, NH)
1645, 1635;
3300, 3200,
3090
1640, 1630;
3320, 3200,
3100
5m
5n
5o
1630; 3350,
3220
0.93 (3Н, s, СН3); 1.08 (3Н, s, СН3); 2.04 (1Н, d, 2J = 18, СН);
2.17 (1Н, d, 2J = 18, СН); 2.61 (2Н, s, СН2); 5.71 (1Н, d, 3J = 5, СН);
6.58-7.27 (8Н, m, C6H4, C6H3, NH); 8.99 (1H, br. s, NH)
0.96 (3Н, s, СН3); 1.07 (3Н, s, СН3); 2.05 (1Н, d, 2J = 16, СН);
2.17 (1Н, d, 2J = 16, СН); 2.61 (2Н, s, СН2); 5.72 (1Н, d, 3J = 5, СН);
6.64-7.29 (8Н, m, C6H4, C6H3, NH); 9.04 (1H, d, 3J = 5, NH)
1632; 3320,
3200, 3090
1630, 3300,
3210, 3100
1.01 (3Н, s, СН3); 1.05 (3Н, s, СН3); 2.04 (1Н, d, 2J = 16, СН);
2.19 (1Н, d, 2J = 16, СН); 2.24 (2Н, s, СН2); 5.90 (1Н, d, 3J = 5, СН);
6.73-7.30 (7Н, m, C6H3, C4H3S, NH); 9.00 (1H, br. s, NH)
5p
1630;
3330, 3200,
3100-3050
0.96 (3Н, s, СН3); 1.08 (3Н, s, СН3); 2.04 (1Н, d, 2J = 16, СН);
2.16 (1Н, d, 2J = 16, СН); 2.53 (2Н, s, СН2);
5.73 (2Н, m, C4H3O, СН); 6.12 (1H, m, C4H3O);
6.71-7.38 (5Н, m, C6H3, C4H3O, NH); 8.93 (1H, br. s, NH)
5q
5r
1635;
3350, 3240,
3100-3050
1.01 (3Н, s, СН3); 1.06 (3Н, s, СН3); 2.05 (1Н, d, 2J = 18, СН);
2.18 (1Н, d, 2J = 18, СН); 2.52 (2Н, s, СН2); 5.99 (1Н, d, 3J = 6, СН);
6.79-7.58 (6Н, m, C6H3, C4H3S, NH); 7.97 (1H, d, 4J = 2, C6H3);
9.17 (1H, br. s, NH)
1631;
3330, 3200,
3100-3050
0.92 (3Н, s, СН3); 1.03 (3Н, s, СН3); 2.02 (1Н, d, 2J = 18, СН);
2.16 (1Н, d, 2J = 18, СН); 2.52 (2Н, s, СН2); 5.81 (2Н, m, C4H3N, СН);
6.12 (1H, m, C4H3O); 6.82 (1Н, d, 3J = 8, C6H3);
7.43-7.58 (2Н, m, C4H3O, NH); 7.62 (1Н, dd, 3J = 8, 4J = 2, C6H3);
7.97 (1Н, d, 4J = 2, C6H3); 9.12 (1H, br. s, NH)
5s
1630;
3300, 3210,
3100
1.05 (3Н, s, СН3); 1.12 (3Н, s, СН3); 2.23 (2Н, s, СН2);
2.52 (2Н, s, СН2); 3.67 (3Н, s, OCH3); 3.81 (3Н, s, OCH3);
4.96 (1H, br. s, NH); 5.72 (1H, br. s, СН); 6.62 (3H, m, C6H3);
7.18 (1H, s, C6H2); 7.43 (1H, s, C6H2); 8.43 (1H, br. s, NH)
5t
1632;
3340, 3200,
3100
1.12 (3Н, s, СН3); 1.15 (3Н, s, СН3); 2.25 (2Н, s, СН2);
2.61 (2Н, s, СН2); 5.87 (1Н, s, CH); 6.47-6.83 (4Н, m, C6H3, NH);
6.85 (1H, s, C6H2); 7.47 (1H, s, C6H2); 8.61 (1H, br. s, NH)
5u
1630;
3320, 3220,
3100
1.06 (3Н, s, СН3); 1.07 (3Н, s, СН3); 2.21 (2Н, s, СН2);
2.61 (2Н, s, СН2); 5.78 (1Н, d, 3J = 5, CH); 6.66 (1Н, d, 3J = 5, NH);
6.84 (1H, s, C6H2); 7.27 (1H, s, C6H2); 7.28-7.45 (2Н, m, C5H4N);
8.36 (2H, m, C5H4N); 9.06 (1H, br. s, NH)
11-(2-Pyridyl)- (5b), 11-(3-Pyridyl)- (5c), 11-(4-Pyridyl)- (5d), 7-Methoxycarbonyl-11-(3-pyridyl)-
(5g), 7-Methoxycarbonyl-11-(4-pyridyl)- (5h), 7-Benzoyl-11-(4-pyridyl)- (5j), 7,8-Dichloro-11-(4-pyridyl)-
(5u)
3,3-dimethyl-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e][1,4]diazepin-1-ones.
The
corresponding
enaminone 3 (3 mmol) and pyridine carbaldehyde (3 mmol) were boiled in ethanol (40 ml) in the presence of
conc. H2SO4 (0.15 ml) for 3 h. Ethanol (25-30 ml) was distilled off on a rotary evaporator, water (40 ml) was
added, and the mixture was neutralized with a concentrated aqueous solution of NaHCO3. The precipitate was
filtered out and recrystallized from 2-propanol.
953

11-(3,5-Difluorophenyl)-
7-Methoxycarbonyl-11-(3,5-difluorophenyl)-
(5a),
7-Methoxycarbonyl-11-(3,4-methylenedioxyphenyl)-
(5f), 7,8-Dichloro-11-(3,4-dimethoxyphenyl)-
(5e),
(5s),
7,8-Dichloro-11-(3,5-difluoro)- (5t) 3,3-dimethyl-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e][1,4]diazepin-1-
ones. Enaminone 3 (3 mmol) and the corresponding aldehyde 4 (2.5 mmol) were boiled in ethanol (30 ml) in the
presence of 2 drops of conc. H2SO4 for 2.5 h; half the volume of the ethanol was driven off on a rotary
evaporator and the mixture was placed in a refrigerator for 24 hours. Water (1-2 ml) was added as needed. The
precipitate was filtered out and recrystallized from ethanol (compounds 5a,s), 2-propanol (compounds 5e,f), or
THF (compound 5t).
3,3-Dimethyl-7-nitro-11-(2-thienyl)-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e][1,4]diazepin-1-one (5q).
Enaminone 3e (3 mmol) and thiophene-2-carbaldehyde 4j (3 mmol) were boiled in ethanol (30 ml) in the
presence of conc. H2SO4 (0.15 ml) for 4 h. The mixture was poured into crushed ice and then the precipitate of
dibenzodiazepine was filtered out and recrystallized from 2-propanol.
7-Benzoyl- (5l), 7-Trifluoromethyl- (5p), 7-Nitro- (5r) 3,3-dimethyl-11-(2-furyl)-1,2,3,4,10,11-
hexahydro-5H-dibenzo[b,e][1,4]diazepin-1-ones. A mixture of enaminone 3 (2 mmol), furfural (2 mmol),
glacial CH3COOH (0.3 ml), and piperidine (0.4 ml) were boiled for 3 h in ethanol (30 ml). The mixture was
cooled and poured into crushed ice. The precipitate was filtered out and recrystallized from toluene.
7-Benzoyl-11-(3-nitrophenyl)- (5i), 7-Benzoyl-11-(2-thienyl)- (5k), 11-(4-Chlorophenyl)-7-
trifluoromethyl- (5m), 7-Trifluoromethyl-11-(4-fluorophenyl)- (5n), 11-(2-Thienyl)-7-trifluoromethyl- (5o)
3,3-dimethyl-1,2,3,4,10,11-hexahydro-5H-dibenzo[b,e][1,4]diazepin-1-ones. A mixture of enaminone 3c,d (2
mmol) and the corresponding aldehyde 4 (2 mmol) were boiled for 3 h in ethanol (30 ml) in the presence of
conc. H2SO4 (0.15 ml). The mixture was cooled and poured into crushed ice. The precipitate of dibenzodiazepine
was filtered out and recrystallized from toluene.
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