Synthesis and some reactions of functionalized 11,12-dihydro-5H-dibenzo[b,g]azonines

Article abstract of DOI:10.1515/znb-2014-0271

Dihydro-5H-dibenzo[b,g]azonine-6,13-dione (2) has been used as a precursor in the synthesis of the indolo[2,3-e]dibenzo[b,g]azonine and tribenzo[b,g,j][1,6] diazacyclododecine ring systems 6 and 7 respectively via a Fischer indolization/periodate oxidatio

Full text of DOI:10.1515/znb-2014-0271

Z. Naturforsch. 2015; aop
Elsayed M. Afsah*, Ahmed A. Fadda, Samir Bondock and Mohamed M. Hammouda
Synthesis and some reactions of functionalized
11,12-dihydro-5H-dibenzo[b,g]azonines
Abstract:
Dihydro-5H-dibenzo[b,g]azonine-6,13-dione
In view of this, and in connection with our studies in
(2) has been used as a precursor in the synthesis of the this area [8], we report here on the synthesis and some
indolo[2,3-e]dibenzo[b,g]azonine and tribenzo[b,g,j][1,6] reactions of the title compounds which possess consider-
diazacyclododecine ring systems 6 and 7 respectively able synthetic and pharmaceutical interest.
via a Fischer indolization/periodate oxidation sequence.
Fischer indolization of the (1,4-phenylenedihydrazono)
derivative 8 gave the polycyclic system 9. The Schmidt
reaction of 2 led to the formation of the benzimidazo[1,2-b] 2 Results and discussion
[2]benzazepine ring system 11. The Mannich reaction of 2
led to the spirocyclic system 15. The reactions of 2 with According to an earlier report [22], the periodate oxida-
aldimines and aromatic aldehydes were also investigated. tion of 5,6-dihydro-11H-benzo[a]carbazole (1) afforded
11,12-dihydro-5H-dibenzo[b,g]azonine-6,13-dione (2).
Keywords: dibenzo[b,g]azonines; indolo-dibenzo[b,g] The present work is concerned with attempts to extend
azonines; Mannich bases; periodate oxidation.
the scope of the periodate oxidation of indoles to
include the indolo-dibenzo[b,g]azonines, as a route to
higher heterocyclic systems (Scheme 1). Attempted syn-
thesis of the indolo-dibenzo[b,g]azonine system 4 via
acid-catalyzed Fischer indolization of the phenylhydra-
zone 3 yielded a dark-red gummy product, which was
difficult to purify.
DOI 10.1515/znb-2014-0271
Received December 24, 2014; accepted January 23, 2015
In an alternative route to the indolo-dibenzo[b,g]
azonine ring system, compound 2 was treated with diazo-
tized aniline or p-toluidine to give 12-(arylhydrazono)-
1 Introduction
The azonine ring system has been the object of consider-
able synthetic efforts [1–8], because this system is present
as a part in various alkaloids. A number of azonines and
benzoazonines have been studied with interest centered
on their potential pharmaceutical activity as antima-
larials [9], analgesics [10], antihypertensive [11] and CNS
activity [12].
The dibenzo[d,fꢀ]azonine ring system is the main part
in the laurifonine, laurifine and laurifinine alkaloids [13].
The azonine core is present in the vinblastine and vincris-
tine alkaloids [14, 15] which possess significant antitumor
activity and have been widely used clinically. However,
the literature on benzoazonines, dibenzoazonines, azoni-
noindoles and related compounds is relatively limited
[16–21].
11,12-dihydro-5H-dibenzo[b,g]azonine-6,13-diones
(5a,
b). Fischer indolization of 5b afforded a single product
which was identified as 5,6-dihydro-15-methyl-indolo[2,3-
e]dibenzo[b,g]azonine-5,11-dione (6). The periodate oxi-
dation of 6 took place quite smoothly and provided a
convenient access to the generation of the functionalized
12-membered macrocyclic system 7. The mass spectrum of
7 showed the molecular ion at m/z ꢁ=ꢁ 384 (19 %).
In the course of our investigation, the coupling
reaction of 2 with bis(diazotized) p-phenylenediamine
afforded 12,12′-(1,4-phenylenedihydrazono)-bis(11,12-dihy-
dro-5H-dibenzo-[b,g]azonine-6,13-dione) (8), which was
subjected to Fischer indolization to afford 9 (Scheme 2).
However, the periodate oxidation of 9 was not feasible
due to its insolubility in commonly used solvents.
On the other hand, an attempt to prepare the
dibenzo[1,4]diazecine ring system 10 by treating 2 with
hydrazoic acid under Schmidt reaction conditions led to
the formation of 1,2-dihydro-9H-benzimidazo[1,2-b][2]
benzazepin-9-one (11), via in situ cyclodehydration of 10,
as confirmed by analytical and spectral data (Scheme 3).
*Corresponding author: Elsayed M. Afsah, Faculty of Science,
Chemistry Department, Mansoura University, ET-35516, Mansoura,
Egypt, e-mail: emafsah@yahoo.com
Ahmed A. Fadda, Samir Bondock and Mohamed M. Hammouda:
Faculty of Science, Chemistry Department, Mansoura University,
ET-35516, Mansoura, Egypt
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2ꢀ
ꢀE. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azonines
X
azonine-2,7-dione, respectively. In addition, there is much
IO4
evidence that bulky substituents at the α-position exert
stereocontrol on the reaction [25–28].
N
H
N
H
1
O
In connection with our studies in the area of Mannich
bases [8, 29–33] and in view of the widespread and increas-
ing interest in the biological activities of Mannich bases
and related compounds, we investigated the Mannich
reaction of 2 with piperidine and formaldehyde anticipat-
ing the formation of the Mannich base 12. Unexpectedly,
however, it gave a product which was identified as the spi-
rocyclic system 14 (Scheme 4).
The formation of 14 may be attributed to the spon-
taneous deamination of 12 to give 13, which undergoes
Diels–Alder dimerization to afford 14. This result is in line
with the reported formation of spirocyclic systems by the
Mannich reaction with tetrahydro-1H-benzo[b]azonine-
2,7-dione [8], thiochromanone [34] and [1]benzazepin-
2,5-(3H,4H)-dione [35].
2: X = O
3: X = NNHPh
O
H+
Fischer indolization
3
NH
2
ArN2+ Cl−
N
H
4
H+
5b
Fischer
NNH Ar
O
O
indolization
Me
NH
N
N
H
O
H
O
5a: Ar = Ph
5b: Ar = C6H4-4-Me
6
IO4
O
O
Me
NH
On the other hand, the reaction of aldimines with
cycloalkanones has opened routes to the corresponding
Mannich bases [30, 36–38]. However, the attempted reac-
tion of benzalaniline with 2 failed to give the expected
base 15, leading instead to the formation of 10-phe-
nylamino-11H-indeno[1,2-b]quinoline (17) (Scheme 5). The
HN
7
O
O
Scheme 1:ꢀSynthesis of indolo[2,3-e]dibenzo[b,g]azonine-5,
11-dione (6) and its oxidation to 7.
IR spectrum of 17 revealed the absence of carbonyl groups
−1
The mass spectrum of 11 indicated the molecular and showed a strong band at 3456 cm (NH). Its mass
1
ion peak at m/z ꢁ=ꢁ 248 (25 %) and the H NMR spectrum spectrum exhibited a molecular ion peak at m/z ꢁ=ꢁ 308
revealed two triplets at δ ꢁ=ꢁ 3.25 (1-H2) and 3.28 (2-H2). In (31 %), and the 1H NMR spectrum revealed two singlets at
addition, the 13C NMR spectrum displays signals at δ ꢁ=ꢁ δ ꢁ=ꢁ 2.40 (10-H2) and 2.92 (NH). The formation of 17 rather
25.62 (C-2), 28.61 (C-1), 142.55 (C-2a) and 172.34 (CO). The than 15 may be attributed to the tendency of 2 to cyclize
assignment of the NH group between the CO group and readily under mild basic conditions to give 5H-indeno[1,2-
the aryl moiety of 10 is based on previous studies on the b]quinolin-10(11H)-one (16), which reacted with aniline,
Schmidt rearrangement [23, 24], and also by analogy resulting from decomposition of benzalaniline, to afford
with the formation of tetrahydro-1H-benzo[b]azocin-2- 17 (Scheme 5).
one [25] and hexahydro-benzo[b][1,4]diazecin-2,7-dione
[8] from 1-benzosuberone and tetrahydro-1H-benzo[b] of
These results are analogous to the formation
9-phenylamino-1H-cyclopenta[b]quinoline from
O
O
2Cl−
N2
NH
N2
N-NH
NH-N
HN
2
O
O
8
H+
Fischer
indolization
O
H
O
N
HN
O
NH
N
H
O
9
Scheme 2:ꢀFischer indolization of the 1,4-phenylenedihydrazono derivative 8.
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ꢂ3
E. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azoninesꢂ
O
2
N
PhCHO/OH−
10 min
−
3/H+
H
HN
2O
PhCHO
HN
2
N
piperidine
2 hrs
N
O
H
O
10
11
HO
O
Ph
Ph
O
Scheme 3:ꢀSchmidt reaction of 2.
HN
O
HN
CH2
O
19 (33 %)
16 (67 %)
18 (12 %)
16 (52 %)
O
N
+
+
−
Piperidine
H10NH
C5
O
2
CH2O
Scheme 6:ꢀAldol condensation of 2 with benzaldehyde.
N
H
O
N
H
13
12
O
2
Dimerization
HN
O
O
O
(CH2-N=CH-Ar)2 /EtOH
Ar
NH
O
O
O
14
HN
H
N
CH2
Scheme 4:ꢀAttempted Mannich reaction of 2.
N
H
Ar
21: Ar = C6H4-4-OMe
O
O
2
20: Ar = C6H4-4-OMe
Ph
NHPh
O
Scheme 7:ꢀReaction of N,N′-bis(p-anisylidene)ethylenediamine with 2.
PhCH=NPh
2
EtOH
N
H
O
15
be rationalized on the basis of a mechanism which involves
the spontaneous deamination of the bis-(Mannich base)
21 to give 20 as the end product. This reaction is of par-
ticular interest, because it offers access with good yields
to the arylidene derivatives of compound 2.
O
NHPh
PhNH2
N
H
N
16
17
Scheme 5:ꢀReaction of 2 with benzalaniline.
3 Experimental section
tetrahydro-1H-benzo[b]azonine-2,7-dione and benzalani-
line [8]. In this connection, the synthesis of compound All melting points (uncorrected) were determined on a
16 has been achieved in a 45 % yield upon treatment of 2 Gallenkamp electric melting point apparatus (Sanyo Gal-
with aqueous sodium hydroxide at room temperature, and lenkamp, Southborough, UK). Elemental microanalyses
it was identical (m.p. and IR spectrum) to an authentic were carried out on a Carlo Erba 1108 Elemental Analyzer
sample previously prepared by heating of 2 at 180 °C [22]. (Heraeus, Hanau, Germany), at Microanalytical Unit,
In line with this, the base-catalyzed condensation of Faculty of Science, Cairo University. Infrared spectra were
2 with benzaldehyde led to the formation of indenoquin- measured on a Mattson 5000 FTIR spectrometer (Mattson
1
olinone 16 as the main product besides the aldol product Instruments, Inc., Madison, WI, USA). H and 13C NMR
18 or the benzylidene derivative 19, depending on the data were obtained in CDCl3 or [D6]DMSO solution on a
reaction conditions (Scheme 6).
Varian XL 300 MHz instrument (Varian, Inc., California,
In addition, the reaction of compound 2 with N,N′- USA) using TMS as internal standard. Chemical shifts are
bis(p-methoxybenzylidene)ethylenediamine afforded reported in ppm (δ) downfield from internal TMS. Mass
12-(4-methoxybenzylidene)-11,12-dihydro-5H-dibenzo[b,g] spectra were recorded on a GC-MS QP-1000 EX Shimadzu
azonine-6,13-dione (20), as the sole product, rather than instrument (Shimadzu, Tokyo, Japan). The course of the
the expected bis-(Mannich base) 21 (Scheme 7). This may reaction and the purity of the synthesized compounds
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4ꢀ ꢀE. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azonines
were monitored by TLC using EM science silica gel coated 3.4 12-(ꢁp-Tolylhydrazono)-11,12-dihydro-
plates, 0.25 nm, 60 GF 254 (Merck, Germany) with visuali-
5H-dibenzo[b,g]azonine-6,13-dione (5b)
zation by irradiation with an ultraviolet lamp. Compounds
1
7, 8, 9 and 18 are of limited solubility in the common H M.p. 312 °C (dichloromethane). Yield 23 % (dark brown
NMR solvents. Compounds 1 and 2 [22] were prepared as powder). – IR (KBr): ν ꢁ=ꢁ 3420 (NH lactam), 3288 (NH
−1
1
previously described. All chemicals used were of pure hydrazone), 1719 (CO), 1705 (CO), 1210 cm . – H NMR
grade and were purchased from Aldrich (WI, USA).
([D6]DMSO): δ ꢁ=ꢁ 1.45 (s, 2H, 11-H2), 2.20 (s, 3H, Ar-CH3),
7.12–7.53 (m, 12H, aromatic), 9.11 (s, 1H, CONH), 10.12 ppm
(s, 1H, NH hydrazone). – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 369 (9)
+
+
[M] , 278 (2) [M–(C6H4-Me)] , 229 (4), 200 (16), 150 (55), 122
(100). – C23H19N3O2 (369.42) calcd. C 74.78, H 5.18, N 11.37;
found C74.63, H 5.11, N 11.21.
3.1 13-(Phenylhydrazono)-11,12-dihydro-
5H-dibenzo[b,g]azonine-6-one (3)
To a solution of 2 [22] (1 g, 4 mmol) in ethanol (10 mL),
phenylhydrazine (0.43 g, 4 mmol) and acetic acid (0.2 mL)
were added. The reaction mixture was heated on a water 3.5 5,6-Dihydro-15-methyl-indolo[2,3-e]
bath for 5 min, and stirred for 90 min at room temperature.
The product obtained on cooling was filtered and crystal-
dibenzo[b,g]azonine-5,11-dione (6)
lized from ethanol to give 3. M.p. 234 °C. Yield 15 % (yellow This compound was obtained by treating 5b (0.6 g,
leaflets). – IR (KBr): ν ꢁ=ꢁ 3440 (NH lactam), 3379 (NH hydra- 1.6 mmol) with hot 20 % sulfuric acid (6 mL) on a water
−1
zone), 1710 (CO), 1430, 1325, 1121 cm . – C22H19N3O (341.41): bath for 30 min, poured onto water (30 mL) and basified
calcd. C 77.40, H 5.61, N 12.31; found C 77.32, H 5.51, N 12.16. with NH4OH. The product was purified by crystalliza-
tion from DMSO to give 6. M.p. 278 °C. Yield 18 % (dark-
green crystals). – IR (KBr): ν ꢁ=ꢁ 3412 (NH indolic), 3356 (NH
−1
1
3.2 12-(Arylhydrazono)-11,12-dihydro-
5H-dibenzo[b,g]azonine-6,13-diones
(5a, b)
lactam), 1710 (CO), 1685 (CO), 1523, 1335, 1223 cm . – H
NMR ([D6]DMSO): δ ꢁ=ꢁ 2.20 (s, 3H, Ar-CH3), 7.12–7.67 (m,
11H, aromatic), 8.15 (s, 1H, NH indolic), 10.36 ppm (s, 1H,
NH amide). – 13C NMR ([D6]DMSO): δ ꢁ=ꢁ 28.13 (CH3-Ar),
Diazotized aniline or p-toluidine (4 mmol) was added with 113.10, 119.21, 121.14, 125.33, 129.76, 132.14, 135.07, 139.66,
stirringtoacoldsolutionof2(1g,4mmol)inpyridine(15mL). 141.24, 143.16 (all Ar-C), 174 (CO), 182 ppm (CO). – MS (EI,
+
+
The reaction mixture was stirred for 30 min at 5–10 °C and 70 eV): m/z (%) ꢁ=ꢁ 352 (11) [M] , 353 (6) [M + 1] , 291 (14),
for 2 h at room temperature. The product obtained on dilu- 264 (15), 240 (16), 215 (22), 201 (20), 144 (100), 77 (26). –
tion with water was filtered off, dried and purified by pre- C23H16N2O2 (352.39): calcd. C 78.39, H 4.57, N 7.95; found C
parative chromatography on Al2O3 using methanol–diethyl 78.28, H 4.48, N 7.87.
ether (2:1) as eluent to give compounds 5a, b.
3.6 2-Methyltribenzo[b,g,jꢀ][1,6]diazacyclo-
3.3 12-(Phenylhydrazono)-11,12-dihydro-
dodecine-6,7,13,18(5H,12Hꢁ)-tetraone (7)
5H-dibenzo[b,g]azonine-6,13-dione (5a)
A solution of 6 (0.20 g, 0.57 mmol) in pyridine (10 mL) was
M.p. 293 °C (chloroform). Yield 36 % (greenish needles). – added to a solution of sodium periodate (0.25 g, 1.14 mmol)
IR (KBr): ν ꢁ=ꢁ 3409 (NH lactam), 3225 (NH hydrazone), 1710 in water (5 mL). After standing at room temperature for
−1
1
(CO), 1692 (CO), 1333, 1210 cm . – H NMR ([D6]DMSO): 20 h, the solvent was removed at reduced pressure, and
δ ꢁ=ꢁ 1.54 (s, 2H, 11-H2), 7.12–7.53 (m, 13H, aromatic), 9.21 the product obtained was washed successively with water
(s, 1H, CONH), 10.53 ppm (s, 1H, NH hydrazone). – 13C NMR (3 ꢁ×ꢁ 10 mL) and boiling pyridine (3 ꢁ×ꢁ 5 mL) to give 7. M.p. ꢁ>ꢁ
([D6]DMSO): δ ꢁ=ꢁ 32.15 (C-11), 117.11, 119.30, 125.13, 129.07, 300 °C. Yield 32 % (colorless powder). – IR (KBr): ν ꢁ=ꢁ 3445
131.24, 136.44, 141.18 (all Ar-C), 154.51 (Cꢁ=ꢁN), 174.22 (CO), (NH lactam), 1730 (CO), 1710 (CO), 1690 (CO), 1620 (CO),
+
−1
+
182.34 ppm (CO). – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 355 (21) [M] , 1210 cm . – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 385 (5) [M + 1] ,
+
336 (4), 200 (16), 184 (45), 138 (15), 122 (100), 76 (48). – 384 (13) [M] , 369 (40), 310 (100), 309 (80), 249 (17), 203
C22H17N3O2 (355.39): calcd. C 74.35, H 4.82, N 11.82; found C (14), 182 (44), 76 (62). – C23H16N2O4 (384.38): calcd. C 71.87,
74.20, H 4.74, N 11.69.
H 4.20, N 7.29; found C 71.77, H 4.12, N 7.11.
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E. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azoninesꢂ ꢂ5
3.7 12,12′-(1,4-Phenylenedihydrazono)-
3.10 1′H-Spiro[dibenzo[b,g]azonine-12,
3′-dibenzo[b,g]pyrano[2,3-dꢀ]azonine]-
6,10′,13 (2′H, 5H, 9′H,11H,15′Hꢀ)-trione (14)
bis(11,12-dihydro-5H-dibenzo-[b,g]
azonine-6,13-dione) (8)
This compound was obtained from 2 (1 g, 4 mmol) and Asolutionof2(0.50g, 2mmol), piperidine(0.22g, 2.5mmol)
bis(diazotized)-p-phenylenediamine (2 mmol) in pyri- and formaldehyde (0.08 g, 2.6 mmol) in acetic acid (15 mL)
dine (15 mL), following the same procedure as described was heated on a water bath at 90 °C for 30 min. A pale-
above for compounds 5a and b. The product was washed yellow powder separated was filtered and crystallized from
with boiling chloroform–methanol (4:1). M.p. ꢁ>ꢁ 300 °C. ethyl acetate to give 14. M.p. ꢁ>ꢁ 300 °C. Yield 26 % (pale-
Yield 54 % (dark-green powder). – IR (KBr): ν ꢁ=ꢁ 3404 (NH yellow powder). – IR (KBr): ν ꢁ=ꢁ 3456 (NH lactam), 3423 (NH
lactam), 3330 (NH hydrazone), 1709 (CO), 1680 (CO), 1585, lactam), 1730 (CO), 1722 (CO), 1693 (CO), 1344, 1282, 1115
−1
+
−1
1315, 1210 cm . – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 632 (5) [M] , cm . – 1H NMR ([D6]DMSO): δ ꢁ=ꢁ 2.31(m, 4H, CH2CH2), 2.71
+
629 (4) [M] , 232 (100), 214 (7), 210 (10), 184 (11), 136 (18). (m, 2H, CH2) 2.82 (m, 2H, CH2), 7.45–8.15 (m, 16H, aromatic),
– C38H28N6O4 (632.67): calcd. C 72.14, H 4.46, N 13.28; found 9.10 (s, 1H, CONH), 9.61 ppm (s, 1H, CONH). – 13C NMR ([D6]
C 72.07, H 4.34, N 13.12.
DMSO): δ ꢁ=ꢁ 24.54, 27.23, 29.14, 32.14 (4 ꢁ×ꢁ CH2), 84.51 (spiro
C), 94.45 (olefinic C), 118.72, 120.18, 122.48, 123.14, 125.68,
126.24, 127.08, 127.54, 128.12, 128.77, 129.37, 129.79, 130.54,
131.11, 132.38, 132.71, 134.07, 135.52, 136.70, 137.64, 139.15,
140.51, 141.11, 142.83 (all Ar-C), 146.21 (olefinic C), 172.12
(CONH),175.08 (CONH),186.41 ppm (CO). – MS (EI, 70 eV):
m/z (%) ꢁ=ꢁ 526 (4) [M] , 508 (21) [M–18] , 232 (14), 214 (28),
186 (70), 146 (40), 120 (56), 105 (7), 92 (50), 77 (25), 50 (100).
– C34H26N2O4 (526.58): calcd. C 77.55, H 4.98, N 5.32; found C
77.49, H 4.86, N 5.28.
3.8 Fischer indolization of 8: synthesis of 9
A mixture of 8 (0.30 g, 0.47 mmol) and 20 % sulfuric acid
(5 mL) was heated on a water bath for 30 min, poured onto
water (20 mL) and basified with NH4OH. The product was
filtered and washed with boiling pyridine to give 9. M.p. ꢁ>ꢁ
300 °C. Yield 33 % (dark-brown powder). – IR (KBr): ν ꢁ=ꢁ
3405 (NH indolic), 3420 (NH lactam), 1712 (CO), 1683 (CO),
+
+
−1
+
1322, 1212 cm . – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 598 (5) [M] ,
473 (27), 324 (18), 260 (26), 216 (20), 232 (100), 166 (35), 154
(21), 92 (17). – C38H22N4O4 (598.61): calcd. C 76.24, H 3.70, N
9.36; found C 76.12, H 3.64, N 9.24.
3.11 5H-Indeno[1,2-b]quinolin-10(11H)-one (16)
Compound 2 (1 g, 4 mmol) was dissolved in cold sodium
hydroxide solution (8 %, 15 mL); a yellow solution was
obtained which after a few seconds warmed up slightly
and became colorless. On neutralization with dilute HCl,
a colorless powder was obtained, which was filtered and
crystallized from ethyl acetate to give 16. M.p. ꢁ>ꢁ 300 °C
3.9 1,2-Dihydro-9H-benzimidazo[1,2-b][2]
benzazepin-9-one (11)
(ꢁ>ꢁ 300 °C [22]). Yield 35 % (colorless powder). – IR (KBr):
To a solution of 2 (0.5 g, 2 mmol) in chloroform (30 mL) ν ꢁ=ꢁ 3456 (NH), 1625 (CO), 1344, 1282, 1115 cm . – 1H NMR
containing 90 % sulfuric acid (4 mL) at 0 °C was added ([D6]DMSO): δ ꢁ=ꢁ 2.42 (s, 2H, CH2), 3.5 (bs, 1H, NH), 7.45–
sodium azide (0.13 g, 2 mmol). After stirring for 1 h at 0 °C 7.92 ppm (m, 8H, aromatic). – 13C NMR ([D6]DMSO): δ ꢁ=ꢁ
and 4 h at 25 °C, the reaction mixture was diluted with ice 35.27 (CH2), 101.15 (olefinic C), 117.21, 119.42, 120.71, 125.15,
water (50 mL) and basified with NH4OH. The product was 127.14, 128.64, 129.07, 130.35, 131.54, 134.04, 142.24, 145.92
filtered and crystallized from ethyl acetate–diethyl ether (all Ar-C), 152.85 (olefinic C), 182.16 ppm (CO). – MS (EI, 70
−1
+
(2:1) to give 11. M.p. 116 °C. Yield 54 % (colorless powder). – eV): m/z (%) ꢁ=ꢁ 232 (100) [M] , 204 (69) 128(14), 214 (28),
IR (KBr): ν ꢁ=ꢁ 1683 (CO), 1597, 1550, 1315, 1212 cm . – 1H NMR 101 (19), 92 (7), 77 (79).
−1
([D6]DMSO): δ ꢁ=ꢁ 3.25 (t, J ꢁ=ꢁ 7.5 Hz, 2H, 1-H2), 3.28 (t, J ꢁ=ꢁ 7. 5
Hz, 2H, 2-H2), 7.35–8.41 ppm (m, 8H, aromatic). – 13C NMR
([D6]DMSO): δ ꢁ=ꢁ 25.62 (C-2), 28.61 (C-1), 116.12, 124.33, 127.14, 3.12 10-Phenylamino-11H-indeno[1,2-b]
128.53, 129.73, 131.24, 136.27, 139.44, 140.88 (all Ar-C), 142.55
quinoline (17)
(C-2a), 172.34 ppm (CO). – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 248
+
(25) [M] , 247 (75), 218 (25), 145 (12), 134 (9), 118 (35), 108 A solution of 2 (1 g, 4 mmol) and benzalaniline (0.73 g,
(12),105 (2.5), 93 (9), 89 (100). – C16H12N2O (248.28): calcd. C 4 mmol) in ethanol (15 mL) and one drop of concentrated
77.40, H 4.87, N 11.28; found C 77.32, H 4.74, N 11.13.
hydrochloric acid was heated on a water bath for 5 min.
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ꢀꢀꢀꢁ
6ꢀ ꢀE. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azonines
After standing at room temperature for 8 h and neutrali- 6.90–7.40 (m, 13H, aromatic), 9.20 ppm (s,1H, CONH). – 13C
zation with NH4OH, the solvent was removed at reduced NMR ([D6]DMSO): δ ꢁ=ꢁ 33.54 (CH2), 119.14, 120.18, 121.64,
pressure, and the product was crystallized from ethyl 123.73, 124.48, 125.53, 127.41, 128.50, 130.75, 131.09, 131.89,
acetate to give 17. M.p. ꢁ>ꢁ 300 °C. Yield 45 % (pale-yellow 133.35, 135.47, 136.94, 137.37, 138.67, 139.44, 140.17, 140.69,
−1
powder). – IR (KBr): ν ꢁ=ꢁ 3456 (NH), 1344, 1282, 1115 cm . 141.15 (all Ar and olefinic C), 171.79 (CONH), 189.04 ppm
1
+
– H NMR ([D6]DMSO): δ ꢁ=ꢁ 2.39 (s, 2H, CH2), 2.92 (bs, 1H, (CO). – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 339 (16) [M] , 200 (94),
NH), 7.50–7.59 ppm (m, 13H, aromatic). – 13C NMR ([D6] 170 (12), 91 (53), 77 (12), 55 (100). – C23H17NO2 (339.38):
DMSO): δ ꢁ=ꢁ 32.44 (CH2), 116.76, 117.54, 120.46, 121.42, calcd. C 81.39, H 5.05, N 4.13; found C 81.27, H 4.88, N 4.05.
124.08, 126.27, 128.51, 129.70, 132.11, 134.48, 136.22, 137.10,
The second product was identified as compound 16.
138.57, 139.34, 140.04, 140.52, 142.36, 143.61, 144.70, 145.17 M.p. ꢁ>ꢁ 300 °C (ethyl acetate). Yield 67 %. It was identical
(all Ar-C), 162.48 ppm (Cꢁ=ꢁN). – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ (m.p. IR and 1H NMR spectra) to an authentic sample pre-
+
+
308 (31) [M] , 290 (7) [M–18] , 258 (26), 232 (100), 186 viously prepared [22].
(70), 146 (40), 120 (56), 105 (7), 92 (50), 77 (25), 50 (100).
– C22H16N2 (308.38): calcd. C 85.69, H 5.23, N 9.08; found C
85.58, H 5.16, N 8.87.
3.15 12-(4-Methoxybenzylidene)-11,
12-dihydro-5H-dibenzo[b,g]azonine-6,
13-dione (20)
3.13 12-[Hydroxyl(phenyl)methyl]-11,
12-dihydro-5H-dibenzo[b,g]azonine-6,
13-dione (18)
A
solution of 2 (1.00 g, 4 mmol) and N,N′-bis
(4-methoxybenzylidene)ethane-1,2-diamine (0.59 g, 2 mmol)
in ethanol (15 mL) and two drops of concentrated HCl
A solution of 2 (1.00 g, 4 mmol) and benzaldehyde (0.42 g, was heated on a water bath for 20 min. After cooling to
4 mmol) in ethanol (15 mL) and two drops of 15 % sodium room temperature the product was crystallized from ethyl
hydroxide solution was warmed on a water bath for 10 min. acetate to give 20. M.p. 293 °C. Yield 45 % (yellow powder).
The product which was separated upon heating was fil- – IR (KBr): ν ꢁ=ꢁ 3456 (NH), 1715 (CO), 1690 (CO), 1344, 1282,
−1
1
tered and crystallized from ethyl acetate to give 18. M.p. ꢁ>ꢁ 1115 cm . – H NMR ([D6]DMSO): δ ꢁ=ꢁ 2.40 (s, 2H, 11-H2),
300 °C. Yield 12 % (pale-yellow powder). – IR (KBr): ν ꢁ=ꢁ 2.92 (bs, 1H, NH), 3.63 (s, 3H, OCH3), 5.42 (s,1H, Ar-CHꢁ=ꢁ),
3550 (OH), 3416 (NH lactam), 1715 (CO), 1693 (CO), 1344, 7.50–7.59 ppm (m, 12H, aromatic). – 13C NMR ([D6]DMSO):
−1
+
1282, 1115 cm . – MS (EI, 70 eV): m/z (%) ꢁ=ꢁ 357 (4) [M] , δ ꢁ=ꢁ 32.42 (CH2), 52.70 (CH3), 115.07, 115.32, 125.41, 125.62,
+
339 (21) [M–18] , 232 (14), 214 (28), 186 (70), 146 (40), 120 126.28, 126.75, 129.57, 130.44, 131.11, 131.45, 132.04, 132.89,
(56), 105 (7), 92 (50), 77 (25), 50 (100). – C23H19NO3 (357.39): 133.38, 134.27, 135.69, 136.33, 138.49, 140.33, 158.89 (all Ar
calcd. C 77.29, H 5.36, N 3.92; found C77.16, H 5.20, N 3.81.
and olefinic C), 171.46 (CONH), 188.74 ppm (CO). – MS
+
Neutralization of the filtrate after separation of 18 (EI, 70 eV): m/z (%) ꢁ=ꢁ 369 (31) [M] , 290 (7), 258 (26), 232
with dilute HCl gave compound 16. M.p. ꢁ>ꢁ 300 °C. Yield (100), 186 (70), 146 (40), 120 (56), 105 (7), 92 (50), 77 (25),
1
52 %. It was identical (m.p. IR and H NMR spectra) to an 50 (100). – C24H19NO3 (369.41): calcd. C 78.03, H 5.18, N 3.79;
authentic sample previously prepared [22].
found C 77.86, H 5.05, N 3.66.
3.14 12-Benzylidene-11,12-dihydro-
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E. M. Afsah et al.: Synthesis and some reactions of 11,12-dihydro-5H-dibenzo[b,g]azoninesꢂ ꢂ7
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Z. Naturforsch.ꢂ
ꢂ2015 | Volume x | Issue x(b)
Graphical synopsis
Elsayed M. Afsah, Ahmed A. Fadda,
Samir Bondock and Mohamed M.
Hammouda
Synthesis and some reactions
of functionalized 11,12-dihydro-
5H-dibenzo[b,g]azonines
DOI 10.1515/znb-2014-0271
Z. Naturforsch. 2015; x(x)b: xxx–xxx
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