1344
R. Janciene, Z. Stumbreviciute, A. Vektariene, L. Kosychova, A. Klimavicius,
A. Palaima, and B. Puodziunaite
Vol 46
C), 122.47 (9-C), 125.65, 132.23, 136.38, 145.13, 145.20 (2-
C), 165.44 (CO), 166.19 (CO), 172.21 ppm (4-CO). Anal.
Calcd. for C18H19N3O5: C, 60.50; H, 5.36; N, 11.76. Found:
C, 60.63; H, 5.29; N, 11.65.
(m, 1H, CH), 6.42–6.46 (m, 2H, 6-H, 8-H), 6.81 (m, 1H, 9-H),
7.83 (br s, 1H, NH); 13C NMR: d 17.05 (4-CH3), 41.07 (3-C),
52.80 (q, J ¼ 32.4 Hz, 5-CH2), 61.37 (4-C), 111.82, 112.00,
123.68, 124.49, 126.69, 140.05, 144.93, 173.44 ppm (CO).
Anal. Calcd. for C12H14F3N3O: C, 52.75; H, 5.16; N, 15.38.
Found: C, 52.87; H, 5.24; N, 15.30.
Dimethyl 4,5-dimethyl-2-oxo-2,3,4,5-tetrahydro-1H-[1,4]
diazepino[2,3-h]quinoline-8,10-dicarboxylate (5g). Dark red
crystals (tert-butylmetyl ether, 20% yield), mp 161–163ꢂC; IR:
9-Amino-4,5-dimethyl-1,3,4,5-tetrahydro-2H-1,5-benzo-
diazepin-2-one (1g). Synthesized from 8g. Cream crystals
(methanol, 70% yield), mp 213–215ꢂC; IR: 3453, 3367, 3198,
3273, 1730, 1708, 1672 cmꢀ1
;
1H NMR: d 1.38 (d, J ¼ 6.4
Hz, 3H, CH3), 2.56 (ddd, J ¼ 1.0, 7.6, 13.8 Hz, 1H, CH2),
2.84 (dd, J ¼ 4.4, 13.9 Hz, 1H, CH2), 3.07 (s, 3H, CH3), 4.02
(m, 1H, CH), 4.05 (s, 3H, OCH3), 4.06 (s, 3H, OCH3), 7.54
(d, J ¼ 9.4 Hz, 1H, 6-H), 8.52 (s, 1H, 9-H), 8.53 (d, J ¼ 9.4
Hz, 1H, 7-H), 9.24 (br s, 1H, NH); 13C NMR: d 18.37 (4-
CH3), 39.39 (5-CH3), 42.04 (3-C), 52.88 (OCH3), 53.06
(OCH3), 61.07 (4-C), 120.32 (d, J ¼ 171.6 Hz, 9-C), 120.99
(d, J ¼ 168.5 Hz, 7-C), 121.06, 124.35, 124.98 (d, J ¼ 159.6
Hz, 6-C), 135.61, 139.74, 140.55, 146.31, 165.27 (CO), 166.01
(CO), 171.72 ppm (2-CO). Anal. Calcd. for C18H19N3O5: C,
60.50; H, 5.36; N, 11.76. Found: C, 60.79; H, 5.40; N, 11.93.
General procedure for the synthesis of 1b,c,e,g, 6 and
7. In a hydrogenation apparatus, equipped with a magnetic stir-
rer, the catalyst 10% palladium on carbon (10% of the weight of
the starting nitroderivative) was added to a solution of suitable
nitrobenzodiazepinone 8b,c,e,g, 9 and 10 (20.0 mmol) in 150–
200 mL of methanol and the mixture was hydrogenated at room
temperature and atmospheric pressure. After the consumption of
1.34 L (60 mmol) of hydrogen the catalyst was filtered off. The
filtrate was concentrated to dryness in vacuum and the resultant
solid residue was crystallized from a proper solvent.
1
1678 cmꢀ1; H NMR: d 1.09 (d, J ¼ 6.1 Hz, 3H, CH3), 2.24
(dd, J ¼ 10.0, 12.6 Hz, 1H, CH2), 2.42 (ddd, J ¼ 1.2, 5.4,
12.6 Hz, 1H, CH2), 2.77 (s, 3H, CH3), 3.86 (m, 1H, CH), 3.95
(br s, 2H, NH2), 6.45–6.51 (m, 2H, 6-H, 8-H), 6.98 (dd, J ¼
8.0, 8.0 Hz, 1H, 7-H), 8.34 (br s, 1H, NH); 13C NMR: d 15.78
(4-CH3), 38.65 (5-CH3), 41.52 (3-C), 62.83 (4-C), 110.53,
111.84, 119.72, 126.29, 139.59, 142.66, 174.76 ppm (CO).
Anal. Calcd. for C11H15N3O: C, 64.34; H, 7.37; N, 20.47.
Found: C, 64.47; H, 7.29; N, 20.59.
5-Acetyl-7-amino-3-methyl-1,3,4,5-tetrahydro-2H-1,5-ben-
zodiazepin-2-one (6). Synthesized from 9. Yellow crystals (ace-
tonitrile, 89% yield), mp 191–193ꢂC; IR: 3438, 3348, 3233,
1
1673, 1653 cmꢀ1; H NMR: d 1.11 (d, J ¼ 6.7 Hz, 3H, CH3),
1.86 (br s, 3H, CH3), 2.75 (m, 1H, CH), 3.46 (dd, J ¼ 6.9, 13.5
Hz, 1H, CH2), 3.83 (br s, 2H, NH2), 4.56 (dd, J ¼ 12.3, 13.1 Hz,
1H, CH2), 6.51 (d, J ¼ 2.5 Hz, 1H, 6-H), 6.67 (dd, J ¼ 2.5, 8.4
Hz, 1H, 8-H), 6.94 (d, J ¼ 8.5 Hz, 1H, 9-H), 7.90 (br s, 1H, NH);
13C NMR: d 12.51 (4-CH3), 22.66 (5-CH3), 34.88(3-C), 54.74
(4-C), 115.06, 115.39, 124.35, 126.05, 135.66, 145.29, 170.38,
175.20 ppm. Anal. Calcd. for C12H15N3O2: C, 61.79; H, 6.48; N,
18.01. Found: C, 61.62; H, 6.41; N, 18.13.
7-Amino-1,4-dimethyl-1,3,4,5-tetrahydro-2H-1,5-benzo-
diazepin-2-one (1b). Synthesized from 8b [11]. Yellowish
crystals (ethyl acetate, 77% yield), mp 149–151ꢂC; 1H NMR:
d 1.24 (d, J ¼ 6.2 Hz, 3H, CH3), 2.28 (dd, J ¼ 7.7, 12.7 Hz,
1H, 3-CH2), 2.51 (dd, J ¼ 5.2, 12.6 Hz, 1H, 3-CH2), 3.13 (br
s, 1H, NH), 3.28 (s, 3H, 1-CH3), 3.66 (br s, 2H, NH2), 4.00
(m, 1H, CH), 6.18 (d, J ¼ 2.5 Hz, 1H, 6-H), 6.36 (dd, J ¼
2.5, 8.4 Hz, 1H, 8-H), 6.91 (d, J ¼ 8.4 Hz, 1H, 9-H); 13C
NMR: d 23.19 (4-CH3), 35.45 (1-CH3), 40.24 (3-C), 56.80 (4-
C), 108.31, 109.43, 123.62, 127.90, 140.15, 144.72, 171.37
ppm (CO). Anal. Calcd. for C11H15N3O: C, 64.34; H, 7.37; N,
20.47. Found: C, 64.38; H, 7.30; N, 20.66.
9-Amino-2,3-dihydro-1H-1,5-benzodiazepin-2-one (7). Syn-
thesized from 10 [10] Yellowish crystals (methanol, 90%
1
yield), mp 170–172ꢂC; H NMR: d 2.39 (s, 3H, CH3), 3.16 (s,
2H, CH2), 3.81 (br s, 2H, NH2), 6.66 (dd, J ¼ 1.4, 7.8 Hz,
1H, 8-H or 6-H), 6.83 (dd, J ¼ 1.3, 8.1 Hz, 1H, 6-H or 8-H),
7.05 (t, J ¼ 7.9 Hz, 1H, 7-H), 8.00 (m, 1H, NH); 13C NMR: d
28.00, 43.80, 113.38, 117.81, 125.54, 138.41, 141.09, 163.09,
166.45 ppm. Anal. Calcd. for C10H11N3O: C, 63.48; H, 5.86;
N, 22.21. Found: C, 63.57; H, 5.79; N, 22.37.
4-Methyl-7-nitro-1-propyl-1,3,4,5-tetrahydro-2H-1,5-ben-
zodiazepin-2-one (8c). To a solution of 2.2 g (10.0 mmol) of
4-methyl-7-nitro-1,3,4,5-tetrahydro-2H-1,5-benzodiazepin-2-one
[12] in 150 mL of benzene, 0.5 g (1.50 mmol) of tetrabutylam-
monium bromide, 15 mL 50% aqueous sodium hydroxide and
1.8 mL (20.0 mmol) of 1-bromopropane were added. The reac-
tion was performed according to the procedure method A pre-
viously described by us [11]. The working-up of the reaction
mixture gave 1.6 g (61%) of 8c. Yellowish crystals (ethyꢀl1 ace-
7-Amino-4-methyl-1-propyl-1,3,4,5-tetrahydro-2H-1,5-
benzodiazepin-2-one (1c). Synthesized from 8c. Beige col-
ored crystals (mixture of methanol and diethyl ether, 71% yielꢀd1),
mp 143-145ꢂC; IR: 3407, 3345, 3330, 3233, 1666–1609 cm
;
1H NMR: d 0.84 (t, J ¼ 7.4 Hz, 3H, CH3), 1.23 (d, J ¼ 6.2 Hz,
3H, CH3), 1.50 (m, 2H, CH2), 2.23 (dd, J ¼ 7.5, 12.6 Hz, 1H, 3-
CH2), 2.48 (dd, J ¼ 5.2, 12.6 Hz, 1H, 3-CH2), 3.05 (br s, 1H,
NH), 3.64 (br s, 2H, NH2), 3.73 (m, 2H, CH2), 3.98 (m, 1H, CH),
6.18 (d, J ¼ 2.5 Hz, 1H, 6-H), 6.35 (dd, J ¼ 2.5, 8.4 Hz, 1H, 8-
H), 6.93 (d, J ¼ 8.4 Hz, 1H, 9-H); 13C NMR: d 11.22 (CH3),
21.13 (CH2), 23.11 (4-CH3), 40.38 (3-C), 49.26 (CH2), 56.89 (4-
C), 108.52, 109.51, 124.08, 126.60, 141.20, 144.74, 171.20 ppm
(CO). Anal. Calcd. for C13H19N3O: C, 66.92; H, 8.21; N, 18.01.
Found: C, 67.23; H, 8.32; N, 17.89.
tate), mp 116–118ꢂC; IR: 3296, 1651, 1517, 1344 cm
;
1H
NMR: d 0.85 (t, J ¼ 7.4 Hz, 3H, CH3), 1.32 (d, J ¼ 6.3 Hz,
3H, CH3), 1.54 (m, 2H, CH2), 2.28 (dd, J ¼ 7.4, 12.9 Hz, 1H,
3-CH2), 2.57 (dd, J ¼ 5.2, 12.9 Hz, 1H, 3-CH2), 3.55 (br s,
1H, NH), 3.86 (m, 2H, CH2), 4.12 (m, 1H, CH), 7.29 (d, J ¼
8.8 Hz, 1H, 9-H), 7.76 (d, J ¼ 2.6 Hz, 1H, 6-H), 7.89 (dd, J ¼
2.5, 8.8 Hz, 1H, 8-H); 13C NMR: d 11.08 (CH3), 21.13(CH2),
23.01(4-CH3), 40.29 (3-C), 49.67 (CH2), 57.32 (4-C), 117.23,
117.84, 123.27, 140.29, 140.78, 145.10, 170.57 ppm (CO).
Anal. Calcd. for C13H17N3O3: C, 59.30; H, 6.51; N, 15.96.
Found: C, 59.61; H, 6.63; N, 16.12.
7-Amino-4-methyl-5(2,2,2-trifluoroethyl)-1,3,4,5-tetrahy-
dro-2H-1,5-benzodiazepin-2-one (1e). Synthesized from 8e
[11]. Yellowish crystals (mixture of diethyl ether and hexane,
95% yield), mp 156–158ꢂC; IR: 3454, 3371, 3174, 1677
1
cmꢀ1; H NMR: d 1.08 (d, J ¼ 6.1 Hz, 3H, CH3), 2.22–2.40
4,5-Dimethyl-9-nitro-1,3,4,5-tetrahydro-2H-1,5-benzodia-
zepin-2-one (8g). To a solution of 2.2 g (10.0 mmol) of dihy-
dro-9-nitroderivative 10 [10] in 50 mL of formic acid, 3.25 g
(m, 2H, CH2), 3.3–3.7 (br s, 2H, NH2), 3.53 (dq, J ¼ 8.9, 15.4
Hz, 1H, 5-CH2), 3.83 (dq, J ¼ 8.6, 15.4 Hz, 1H, 5-CH2), 4.02
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet