Convenient synthesis of 7H-Naphtho-[1,8-gh]quinolin-7-one

Article abstract of DOI:10.1080/00397911.2010.531368

7H-Naphtho[1,8-gh]quinolin-7-one was prepared by the glycerol condensation of 3-aminophenalenone in good yields. This method provides a new and convenient synthesis of the compound. NMR spectra of its related compounds were measured, and the rapid interchange between two equivalent a-enone structures was found, which is well known as the phenomenon for the formation of carboxylic acid dimer or hydrogen difluoride ion. Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397911.2010.531368

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Convenient Synthesis of 7H-Naphtho-
[
1,8-gh]quinolin-7-one
a a
a
Tadanobu Sawada , Hiroyuki Ishii , Yoshitomo Aoyama
,
a
b
b
Toyotoshi Ueda , Junji Aoki & Minoru Takekawa
a
Department of Interdisciplinary Science and Engineering, School of
Science and Engineering, Meisei University, Tokyo, Japan
b
Department of Chemistry, Faculty of Science, Toho University,
Chiba, Japan
Accepted author version posted online: 24 Aug 2011.Version of
record first published: 11 Nov 2011.
To cite this article: Tadanobu Sawada, Hiroyuki Ishii, Yoshitomo Aoyama, Toyotoshi Ueda, Junji Aoki
&
Minoru Takekawa (2012): Convenient Synthesis of 7H-Naphtho-[1,8-gh]quinolin-7-one, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
2:6, 784-793
4
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1
Synthetic Communications , 42: 784–793, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.531368
CONVENIENT SYNTHESIS OF 7H-NAPHTHO-
1,8-gh]QUINOLIN-7-ONE
[
1
Tadanobu Sawada, Hiroyuki Ishii, Yoshitomo Aoyama,
1
1
1
2
Toyotoshi Ueda, Junji Aoki, and Minoru Takekawa
2
1
Department of Interdisciplinary Science and Engineering, School of Science
and Engineering, Meisei University, Tokyo, Japan
2
Department of Chemistry, Faculty of Science, Toho University, Chiba,
Japan
GRAPHICAL ABSTRACT
Abstract 7H-Naphtho[1,8-gh]quinolin-7-one was prepared by the glycerol condensation of
-aminophenalenone in good yields. This method provides a new and convenient synthesis of
3
the compound. NMR spectra of its related compounds were measured, and the rapid inter-
change between two equivalent a-enone structures was found, which is well known as the
phenomenon for the formation of carboxylic acid dimer or hydrogen difluoride ion.
Keywords 3-Aminophenalenone; 11-azabenzanthrone; glycerol condensation; NMR
spectra; rapidly changing couple
INTRODUCTION
7
material because it gives nanocyclic aromatic compounds by self-condensation,
H-Benz[de]anthracen-7-one (benzanthrone, Bz) (1a) is a valuable starting
[
1]
some of which have been used as excellent vat dyes and have been shown to be
[3]
organic semiconductors or photoconductors.
[2]
Azabenzanthrone, in which a carbon atom is replaced by a nitrogen atom, may
also give polycyclics similar to those of 1a and have significant effects on physical or
chemical properties because of the presence of a nitrogen atom.
Previously, we reported the preparation of 1-azabenzanthrone (1NBz) (1b) and
[4]
its condensation products. Since then, we have continued studies on preparing
other azabenzanthrone compounds.
Received March 15, 2010.
Address correspondence to Tadanobu Sawada, Department of Interdisciplinary of Science and
Engineering, School of Science and Engineering, Meisei University, Hodokubo 2-1-1, Hino, Tokyo
191-8506, Japan. E-mail: sawada@ge.meisei-u.ac.jp
7
84

SYNTHESIS OF 11-AZABENZANTHRONE
785
Scheme 1. Molecular structures of Bz, 1NBz, and 11NBz.
Scheme 2. Previous methods of synthesizing 11NBz (1c).
Scheme 3. New method of synthesizing 11NBz (1c).

786
T. SAWADA ET AL.
7H-Naphto[1,8-gh]quinolin-7-one (11-azabenzanthrone, 11NBz) (1c) is a start-
ing material for preparation of diazapolycyclic compounds (Scheme 1). Several
[
5,6]
methods of synthesis have already been reported as shown in Scheme 2,
but these
methods are not easy to perform because of poor yields or long processes. We suc-
ceeded in preparing this compound in good yields by glycerol condensation of
3
-aminophenalen-l-one (5a) obtained from 3-hydroxyphenalen-1-one (4a) as shown
in Scheme 3.
The present aricle describes this method and provides analyses of NMR spectra
of 1c and related compounds 4a and 5a.
RESULTS AND DISCUSSION
3-Hydroxyphenalen-1-one (4a); 2,2-Dihydrophenalene-1,3-dione (4b)
This compound was prepared in a good yield by heating a mixture of
[
naphthalic anhydride (2) and diethylmalonate (3) in the presence of zinc chloride.
7]
[
Compound 4a may exist as a tautomeric form of 4b. The number of H NMR
8]
multiplet signals are shown in Table 1.
The reaction product obtained by the method of Eistert et al. gave 4b type of
[
7]
1
H NMR spectra in dimethylsulfoxide (DMSO-d ), trifluoroacetic acid (TFA-d ),
6
1
and pyridine-d as shown in Fig. 1. However, integral intensity ratio in these con-
5
ditions is singlet–doublet–triplet 1:4:2 except for the OH signal, not 1:2:1. Therefore,
the structure of this reaction product under these conditions was considered to be a
0
couple rapidly interchanging between 4a and 4a . A broad peak of an aromatic
1
hydroxyl group was observed in DMSO-d at 11.77 ppm in the H NMR spectrum
6
0
1
1
for a couple of 4a$4a . In H- H nuclear Overhauser effect spectroscopy (NOESY),
the broad peak was identified as having nuclear Overhauser effect (NOE) corre-
lation with the singlet signal in the 2-position and no correlation with the doublet
0
signal of the 4-position. Therefore, the hydroxyl group in 4a or 4a under DMSO-d
takes the 3-position. The OH signal was broadened drastically and shifted upfield,
but a singlet signal at 6.0 ppm remained with constant shift value and constant
6
ꢀ
band width, as the temperature increased from the room temperature to 90 C. This
result is shown in Fig. 2. It might have symmetric double minimum potential of a
1
Table 1. Numbers of H NMR multiplet signals for 4a and 4b
Singlet
Doublet
Triplet
1
4
2
1
2
1

SYNTHESIS OF 11-AZABENZANTHRONE
787
1
Figure 1. H NMR spectra of 3-hydroxyphenalenone (4a) in DMSO-d
6
, TFA-d
1
, and pyridine-d
5
.
1
Figure 2. H NMR spectra of 3-hydroxyphenalenone (4a) at 19 C, 30 C, 50 C, 70 C, and 90 C.
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ

788
T. SAWADA ET AL.
1
Figure 3. H NMR spectra of 3-aminophenalenone (5a) in DMSO-d
6
and DMSO-d
6
–CD
3
OD ¼ 4:1.
hydrogen atom in the region between C=O. . .X. . .H-O-C and C-O-H. . .X. . .O=C.
X may be either a proton-accepting solvent or hydrogen attached to the second
carbon.
The crystal structure of this compound has been reported by x-ray diffraction
[
9]
(
XRD) analysis. Some researchers reported strong intermolecular hydrogen bonds
1
Figure 4. Two-dimensional NMR spectra of 3-aminophenalenone (5a). (a) H- H COSY; (b) H- H
1
1
1
NOESY.

SYNTHESIS OF 11-AZABENZANTHRONE
789
in the crystal, but we might expect some kind of intermolecular or intramolecular
hydrogen bond in the solution.
From these results, we are greatly inclined to support the rapid interchange
0
between 4a and 4a , resulting in the apparent C symmetry of NMR spectra, which
2
V
[
10,11]
is similar to the phenomenon well known in a dimer of carboxylic acid
[12,13]
hydrogen difluoride ion HF .
or
ꢁ
2
3-Aminophenalen-1-one (5a)
[
14]
Sodolar and Kochkin
ammonium acetate, and they reported that this compound can exist as one of three
prepared this compound by heating 4a with
tautomeric forms [i.e., the amino ketone (5a), the imino ketone (5b), and the
hydroxyl imine (5c] and that a signal for the NH group, corresponding to two
2
1
protons, was found at 7.3 ppm in the H NMR spectrum in DMSO-d , which disap-
6
peared after addition of CD OD. Consequently, they concluded that this compound
3
exists in the form of the amine 5a under the condition for measurement of the spec-
trum. We double-checked this and, in addition, analyzed the structure with
1
1
1
1
two-dimensional (2D) NMR ( H- H COSY and H- H NOESY). Our results, shown
in Figs. 3 and 4, and Table 2, support their conclusion.
11-Azabenzanthrone (1c)
The structure of the product obtained by glycerol condensation of 5a was
1
confirmed by NMR spectra. One-dimensional (1D) NMR spectra ( H, C) are
13
1
13
shown in Figs. 5 and 6. Complete assignment of H and C NMR spectra was
1
1
1
1
13
1
1
13
made with the aid of H- H COSY, H- H NOESY, C- H COSY, and H- C
heteronuclear multiple bond correlation (HMBC) techniques, as given in Fig. 7.
The results of 1D and 2D NMR spectra are shown in Table 3. NOE of 4.6%
1
was found between H signals for 3- and 4-positions in differential NOE. These
results confirmed that this product was 11-azabenzanthrone (1c). In addition, ultra-
violet (UV)–visible spectra of homologs (1a, 1b, and 1c) resemble each other
ꢀ
(Fig. 8), and comparison of the melting points of 1c (168 C) with those of 1a
Table 2. Experimental results of NMR measurements for 3-amino-phenalenone (5a)
ꢀ
at 40 C
H correlation H correlation
in COSY
1
Position
2
H d (ppm) Pattern J (HH) (Hz)
in NOESY
5.782
7.213
8.349
7.668
8.158
8.158
7.698
8.290
s
3 (-NH
2
)
)
3
4
5
6
7
8
9
(-NH
2
)
s
dd
dd
dd
dd
dd
dd
7.4, 0.8
8.2, 7.4
8.2, 0.8
8.0, 1.1
8.0, 7.1
7.1, 1.1
5
4, 6
5
3 (-NH
2
8
7, 9
8

790
T. SAWADA ET AL.
1
Figure 5. H NMR spectra of 11-azabenzanthrone (1c).
ꢀ
[15]
(
point very near that of 1a.
ꢀ
[4]
170 C ) and 1b (181–183 C ) is interesting. Compound 1c showed a melting
The synthesis of 1c by the method described in this article gave considerably
good overall yields of 49% from raw material 2.
13
Figure 6. C NMR spectra of 11-azabenzanthrone (1c).

SYNTHESIS OF 11-AZABENZANTHRONE
791
1
Figure 7. Two-dimensional NMR spectra of 11-azabenzanthrone (1c). (a) H- H COSY, (b) C- H
1
13
1
1 13
COSY, and (c) H- C HMBC.
ꢀ
Table 3. Experimental results of NMR measurements for 11-azabenzanthrone (1c) at 110 C
1
13
C d (ppm)
(CH-COSY)
H d
Position (ppm) Pattern
J (HH) H correlation H correlation in
(Hz)
C correlation
HMBC
in COSY
NOESY
1
2
3
3
4
5
6
6
7
7
8
9
0
9.039
7.829
8.255
d
t
8.0
2
1, 3
2
126.412
126.412
131.232
132.021
135.164
126.115
128.748
126.905
182.049
125.408
134.357
123.088
153.457
151.993
126.510
127.102
3, 11a, 11c
3a, 11b
1, 4, 11c
8.0
8.0
d
4
3
a
8.442 dd
7.876
8.613 dd
8.0, 1.5
8.0
8.0, 1.5
5
4, 6
5
3, 6, 11c
3a, 6a
4, 7, 11c
t
a
a
8.594 dd
7.622 dd
9.002 dd
8.0, 1.5
8.0, 4.5
4.5, 1.5
9
8, 10
9
7, 10, 11a
7a
8
1
1
1
1
1a
1b
1c
EXPERIMENTAL
All melting points were uncorrected. UV-visible absorption spectra were mea-
sured in toluene on a Shimadzu UV-2200A spectrophotometer. Infrared (IR) spectra
were recorded with KBr discs using a Shimadzu FTIR-8300 instrument. NMR spec-
1
13
tra were recorded on a Jeol JNM A-500 spectrometer ( H, 500 MHz; C,
25.7 MHz). All samples were freshly prepared (ca. 5 mg) and dissolved in DMSO-d
1
6
1
13
1
1
1
1
13
1
1
13
0.5 ml). H, C, H- H COSY, and H- H NOESY, C- H COSY, and H- C
(
HMBC were measured in ways similar to those described in the previous paper.
[
16]
3-Hydroxyphenalenone (4a)
Synthesis was carried out by the method similar to that described in Ref. 7.
From 198.2 g (1.000 mol) of naphthalic anhydride (2), 590 ml of diethyl malonate

792
T. SAWADA ET AL.
Figure 8. UV-visible spectral data of 11-azabenzanthrone (1c) and its related compounds (1a and 1b).
(
2
3), and 200 g of zinc chloride was obtained 175.2 g (89%) of yellow powder of 4a, mp
ꢀ
[7]
45–249 C (decomp.) [86–90%, mp 255 C (decomp.)]. Recrystallization from gla-
ꢀ
ꢀ
cial acetic acid gave orange cubic crystals of 4a, mp 247–248 C (decomp.); k
max
(
7
4
ethanol) ¼ 332, 352 nm; IR (KBr) ¼ 2517, 1623, 1514, 1337, 1236, 1224, 1213, 833,
ꢁ
1
1
72 cm
,6,7,9-positions), 7.73 (t, 2H, 5,8-positions), 6.01 (s, 1H, 2-position).
;
H NMR (DMSO-d ) d (ppm) ¼ 11.77 (s, -OH), 8.28–8.24 (d, 4H,
6
3-Aminophenalenone (5a)
A mixture of 19.6 g (0.100 mol) of 4a and 196 g of ammonium acetate was
ꢀ
heated at 140–145 C for 2 h and worked up in a manner similar to that described
in Ref. 9, giving 15.8 g (81%) of orange powder of 5a. Recrystallization from water
ꢀ
ꢀ
[8]
gave orange needles of 5a, mp 235–236 C (235–236 C ); k
4
(
(ethanol) ¼ 338.5,
max
ꢁ
1 1
28.5 nm; IR (KBr) ¼ 3172, 1632, 1551, 1379, 1275, 1238, 831, 767 cm ; H NMR
DMSO-d ) signals are shown in Table 2 and Figs. 3 and 4.
6
11-Azabenzanthrone (1c)
To a solution of 19.5 g (0.100 mol) of 5a and 76.3 g (0.300 mol) of sodium
m-nitrobenzenesulfonate (90%) in 600 g of 82% sulfuric acid was added 29.1 g
ꢀ
(
0.300 mol) of glycerol (95%) under stirring at 95 C in 1 h. The reaction mixture
ꢀ
was further stirred at 135 C for 6 h and poured into a large amount of crushed
ice after being cooled to room temperature. It was neutralized with sodium hydrox-
ide solution, and the resultant precipitate was filtered off, washed with water, and
dried. The reaction product (21.8 g) was refluxed with 200 g of ethanol for 2 h and
cooled to room temperature. The insoluble part was filtered off, and its dry powder
(19.2 g) was extracted with toluene. The extract (17.1 g) was crystallized two times
from glacial acetic acid to give 15.7 g (68%) of yellow needles of 1c, mp 168 C
ꢀ

SYNTHESIS OF 11-AZABENZANTHRONE
793
ꢀ
[5]
ꢀ
[6]
(
(
DSC) (159–160 C , 162 C ); k
(toluene) ¼ 306, 378 nm (see Fig. 8); IR
13
max
ꢁ
1
KBr) ¼ 1653, 1578, 1389, 1356, 1288, 775 cm ; mass calcd. for C H NO:
1
6
9
þ
1
[
shown in Table 3 and Figs. 5–7.
M] ¼ 231.07; found: m=z ¼ 231.05. H and C NMR (DMSO-d ) signals are
6
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