5
76
JARIKOTE et al.
Yields, melting points, and elemental analyses of compounds II–IV
Found, %
H
Calculated, %
H
Comp.
no.
Yield,
%
R
mp, °C
Formula
C
N
C
N
IIa
COOH
OH
79
75
81
77
70
70
78
65
72
67
76
69
80
78
74
268
192
171
221
121
84
60.25
62.78
54.52
64.36
57.20
56.30
58.16
51.14
59.79
53.36
56.30
58.12
51.13
59.89
53.33
4.12
4.70
3.61
5.42
3.70
4.18
4.75
3.71
5.38
3.89
4.15
4.78
3.69
5.35
4.15
06.35
07.30
12.70
06.75
06.51
11.83
13.47
17.69
12.67
12.32
11.88
13.48
17.72
12.63
12.38
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
11
10
10
11
10
11
10
10
11
10
11
10
10
11
10
H
9
NO
NO
4
60.28
62.82
54.55
64.38
57.30
56.41
58.25
51.07
59.99
53.47
56.41
58.25
51.07
59.99
53.47
4.14
4.74
3.66
5.40
3.85
4.30
4.89
3.86
5.49
4.04
4.30
4.89
3.86
5.49
4.04
06.39
07.33
12.72
06.83
06.68
11.96
13.54
17.87
12.72
12.47
11.96
13.54
17.87
12.72
12.47
IIb
H
H
H
H
H
H
H
H
H
H
H
H
H
H
9
8
3
IIc
NO
2
N
2
O
4
IId
OCH
Cl
3
11NO
3
IIe
8 2
ClNO
IIIa
IIIb
IIIc
IIId
IIIe
IVa
IVb
IVc
IVd
IVe
COOH
OH
10
2 4
N O
162
145
253
191
187
205
131
167
178
10
N
2 3
O
NO
2
9
N
3
O
4
OCH
Cl
3
12
N
2
O
3
9
ClN
2
O
2
COOH
OH
10
2 4
N O
10
N
2 3
O
NO
2
9
N
3
O
4
OCH
Cl
3
12
N
2 3
O
2 2
10ClN O
–
1
1
condensation of succinic acid monoanilides Ia–Ie by
the action of polyphosphoric acid in acetic acid. Initial
amides Ia–Ie were obtained in quantitative yield by
treatment of succinic anhydride with the corresponding
substituted anilines [12]. Compounds IIa–IIe reacted
with hydroxylamine hydrochloride to give oximes
IIIa–IIIe in good yield. The latter were subjected to
Beckmann rearrangement by the action of thionyl
chloride in diethyl ether to afford the target benzo-
diazocines IVa–IVe (Scheme 1).
trum, ν, cm : 3280 br.s, 1710, 1690, 1665. H NMR
spectrum (CDCl ), δ, ppm: 2.5 t (2H, 3-H), 2.8 t (2H,
3
4-H), 4.2 s (3H, OCH ), 7.27–8.0 m (4H, H ), 9.40 s
3
arom
(1H, CONH). Compounds IIa–IIc and IIe were syn-
thesized in a similar way.
7
-Methoxy-3,4-dihydro-1H-1-benzazepine-2,5-
dione 5-oxime (IIId). A mixture of 2.05 g (0.01 mol)
of compound IId, 0.7 g (0.01 mol) of hydroxylamine
hydrochloride, 20 ml of ethanol, and 0.5 ml of pyridine
was heated for 20 min under reflux on a water bath.
The solvent was distilled off, the residue was treated
with water (3×5 ml), and the mixture was stirred on
cooling with ice until a solid precipitated. The product
was filtered off, washed with water, and recrystallized
from ethanol. Yield 1.58 g (72%), mp 253°C.
EXPERIMENTAL
The melting points were determined in open
capillary on heating on a paraffin bath and were not
corrected. The IR spectra were recorded in Nujol on
1
a Perkin–Eimer 237 spectrophotometer. The H NMR
8
-Methoxy-1,3,4,6-tetrahydro-1,6-benzodiazo-
spectra were obtained from solutions in CDCl using
3
cine-2,5-dione (IVd). Oxime IIId, 2.2 g (0.01 mol),
was dissolved in 20 ml of dry diethyl ether, 3 ml of
thionyl chloride was added to the solution, and the
mixture was stirred for 30 min. The solvent and excess
thionyl chloride were distilled off, 25 ml of water was
added to the residue, and the mixture was heated at
the boiling point for several minutes. The product was
filtered off, washed, and recrystallized from acetic
acid. Yield 1.51 g (69%), mp 205°C. IR spectrum, ν,
a Perkin–Elmer R-32 spectrometer; the chemical shifts
were measured relative to TMS as internal reference.
7
-Methoxy-3,4-dihydro-1H-1-benzazepine-2,5-
dione (IId). A mixture of 2.23 g (0.01mol) of
-(4-methoxyphenylcarbamoyl)propionic acid, poly-
phosphoric acid prepared from 10 g of P O and 3 ml
3
2
5
of H PO , and 20 ml of acetic acid was heated for 2 h
3
4
at 95–100°C. The mixture was cooled, poured onto
crushed ice, and left to stand for 2 h. The product was
filtered off, washed with water, and recrystallized from
acetic acid. Yield 1.57 g (77%), mp 221°C. IR spec-
–
1
1
cm : 3285, 1680, 1650. H NMR spectrum (CDCl
δ, ppm: 2.7 t (2H, 3-H), 3.0 t (2H, 4-H), 3.9 s (3H,
OCH ), 7.2–8.3 m (4H, Harom), 9.2 s (1H, CONH).
),
3
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 4 2004