Condensation of 1-(dicyanomethylene)acenaphthene-2-one with aromatic diamines

Article abstract of DOI:10.1002/jccs.200800169

1-(Dicyanomethylene)acenaphthene-2-one (1) reacts with 1,8- diaminonaphthalene (2) to yield two products, identified as acenaphtho[1,2-b] naphtho[1,8-ef][1,4]diazepine (3) and (Z)-2-(8-aminonaphthalen-1-ylamino)-2-(2- oxoacenaphthylen-1(2H)-ylidene)aceton

Full text of DOI:10.1002/jccs.200800169

1150
Journal of the Chinese Chemical Society, 2008, 55, 1150-1155
Condensation of 1-(Dicyanomethylene)acenaphthene-2-one with Aromatic
Diamines
Kamal M. El-Shaieb
Chemistry Department, Faculty of Science, Minia University, El-Minia, Egypt
1-(Dicyanomethylene)acenaphthene-2-one (1) reacts with 1,8-diaminonaphthalene (2) to yield two
products, identified as acenaphtho[1,2-b]naphtho[1,8-ef][1,4]diazepine (3) and (Z)-2-(8-aminonaph-
thalen-1-ylamino)-2-(2-oxoacenaphthylen-1(2H)-ylidene)acetonitrile (4). On the other hand, (2Z,2¢Z)-
2,2¢-(hydrazine-1,2-diylidene)diacenaphthylen-1(2H)-one (6) was obtained during the condensation pro-
cess of 1 with hydrazine hydrate (5). Reaction of 1 with 3,4-diaminotoluene (8b) produces 9-methyl-
acenaphtho[1,2-b]quinoxaline (9b) and (Z)-2-(2-amino-5-methylphenyl-amino)-2-(2-oxoacenaph-
thylen-1(2H)-ylidene)acetonitrile (10b). However, treatment of 5,6-diamino-pyrimidine-2,4-diol hemi-
sulphate (11) with 1 affords acenaphtho[1,2-g]pteridine-9,11-diol (12).
Keywords: Acenaphthenequinone; Malononitrile; Diamines; Cyclocondensation; Diazepine;
Pteridine.
INTRODUCTION
Naphthalene and its derivatives have been exten-
attack by Chaetomium globosum, and to prevent growth of
bacteria in food preparations such as diced carrots.10 1-
Methyl-4(4-chlorophenyl)pyrrolo(spiro-[2.2²]acenaph-
thene-1²)spiro[3.3¢]-5¢(4-chloro-phenylmeth-ylidene)-1¢-
methyltetrahydro-4¢-(1H)-pyridinone has been recently
synthesized and its structures were proved by x-ray struc-
ture analysis. The synthesized compound was obtained
from the reaction of equivalent amounts of 1-methyl-3,5-
bis[(E)-4-chlorophenylmethylidene]tetrahydro-4(1H)-
pyridinone with 1 and sarcosine.11 We have spent a long
time on the synthesis of new heterocycles via condensation
reactions1,12 and/or donor-acceptor interaction.13-16 Ac-
cordingly and in this paper, we have prompted to utilize
1-(dicyanomethylene)acenaphthen-2-one (1) in the synthe-
sis of new heterocyclic compounds which might show pro-
spective biological activities.
sively used in organic synthesis especially in the case of do-
nor-acceptor interactions1 to give non-linear optically ac-
tive compounds. The broad spectrum of applications of
acenaphthenequinone and its derivatives as biologically
active compounds has prompted us to review their chemis-
try and uses. In a different manner, acenaphthenequinone
itself reacted with dimethyl acetylenedicarboxylate to give
spiro compounds.2 Moreover, acenaphthenequinone deriv-
atives were found to be a useful intermediate in the manu-
facture of dyes.3-6 Recently, a series of linear, high molecu-
lar weight polymers were synthesized by one-pot, super-
acid-catalyzed reaction of malononitrile ylidene of ace-
naphthenequinone 1 with aromatic hydrocarbons. The
polymer-forming reaction was found to be greatly depend-
ent on the acidity of the reaction medium, as judged from
the viscosity of the polymers obtained.7 Acenaphthenequi-
none has been used to synthesis a series of antibacterial
compounds.8 Azomethines of acenaphthenequinones can
be prepared by condensation of acenaphthenequinone
with organic amines. The resultant products were found to
have fungicidal activity while the acenaphthenquinone-
dialkoximes are useful as anti-inflammatory agents.9 Com-
pound 1 has been also utilized in the treatment of pea seeds
to improve their germination, to protect cotton goods from
RESULTS AND DISCUSSION
Condensation of 1-(dicyanomethylene)acenaph-
thene-2-one (1) with 1,8-diaminonaphthalene (2) in reflux-
ing DMF, gives not only acenaphtho[1,2-b]naphtho[1,8-
ef][1,4]diazepine (3) but also, (Z)-2-(8-aminonaphthalen-
1-ylamino)-2-(2-oxoacenaphthylen-1(2H)-ylidene)aceto-
nitrile (4) (Scheme I). The structures of 3 and 4 were de-
duced from their elemental analyses and their IR, 1H, and
13C NMR spectra. Moreover, the mass spectra of these
* Corresponding author. Tel: +2-086-7831644; Fax: +2-086-2342601; E-mail: kelshaib@hotmail.com

1-(Dicyanomethylene)acenaphthene-2-one
J. Chin. Chem. Soc., Vol. 55, No. 5, 2008 1151
Scheme I Condensation of 1-(dicyanomethylene)acenaphthene-2-one (1) with aromatic diamines
compounds displayed molecular ion peaks at the appropri-
ate m/z values. The product 4 was characterized on the ba-
sis of spectroscopic data. The IR spectrum showed two
strong absorptions due to CºN and C=O at n = 2220 and
1665 cm-1, respectively. The 1H NMR spectrum of 4 dis-
played two doublets at d = 7.22 and 7.71 ppm with coupling
constant (J = 9.1 Hz), in addition to two broad singlets at d
= 4.80, 7.35 ppm ascribable to -NH2 and –NH, respectively.
Moreover, the rest of the aromatic protons resonated as a
triplet at d = 7.82 ppm and two double-doublets at d =
8.54-8.58 and at d = 9.25-9.29 ppm. The 13C NMR spec-
trum of 4 shows two distinguishable carbon signals at d =

1152 J. Chin. Chem. Soc., Vol. 55, No. 5, 2008
El-Shaieb
175.0 (CO), and 117.0 (CºN).
123.7, 127.1, 127.4 and 129.6 ppm. The mass spectrum of
9a displayed two sharp peaks at m/z = 254 and 127 charac-
teristic for the molecular ion peak (M+) and disubstituted
naphthalene with the molecular formula (C10H6), respec-
tively. Furthermore, IR, NMR and MS gave strong evi-
dence for the formation of 10a as well.
It was previously reported that direct reaction of 1
with hydrazine hydrate (5) gave 9-aminoacenaphtho[1,2-
c]pyridazine-10-carbonitrile.19 However, when we had car-
ried out this experiment by heating 1 with 5 in DMF under
reflux conditions for 5 h we got (2Z,2¢Z)-2,2¢-(hydrazine-
1,2-diylidene)diacenaphthylen-1(2H)-one (6). The IR spec-
tra showed two sharp peaks at n = 1711 and 1640 cm-1 char-
acteristic for (CO) and (C=N) groups, respectively, while
the 1H NMR spectrum revealed the aromatic protons as one
multiplet at d = 7.65-7.55 ppm distinguishing four protons,
one singlet at d = 7.45 ppm, one double doublets at d =
7.75-7.71 ppm in addition to two doublets at d = 7.89 and
8.16 ppm and each had the integration of two protons.
The 13C NMR spectrum of 6 showed twelve distinct
resonances at d = 114.4 (CH), 121.8 (CH), 123.1 (CH),
125.9 (CH), 127.3 (CH), 127.6 (CH), 128.2 (C), 130.1 (C),
133.8 (C), 134.8 (C), 136.0 (C), 142.4 (CO) in agreement
with the proposed structure. Mass spectra and elemental
analyses established the molecular formula of 6 as
C24H12N2O2.
On the other hand, both 9-methyl-acenaphtho[1,2-
b]quinoxaline (9b) and (Z)-2-(2-amino-5-methyl phenyl-
amino)-2-(2-oxoacenaphthylen-1(2H)-ylidene)acetoni-
trile (10b) were produced on heating compound 1 with
3,4-diaminotoluene (8b) in EtOH. The formation of com-
pound 10b not 13b is the result of the postulate that at first
the amino group with the higher electron density reacts pre-
dominantly.17-20 The structural assignment of 9b was sup-
ported by the following spectral data: in its 13C NMR spec-
trum, the characteristic absorption signal of the C=N atoms
appeared at d = 153.3, 152.6 ppm. The methyl carbon reso-
nates in the 1H NMR spectrum of 9bat d = 21.2 ppm. More-
over the 1H NMR spectrum of 9b showed the aromatic pro-
tons through a range of d = 7.67-8.42 ppm. Additionally a
signal at d = 2.61 ppm appeared due to the resonance of
methyl protons. The formation of 9b was further confirmed
by mass spectrometry and elemental analyses. However,
the structure of compound 9b was established by its spec-
tral data. On the other hand, it can be shown that the mass
spectra and elemental analysis of 10b established the mo-
lecular formula as C21H15N3O. While its IR spectrum showed
two sharp absorptions at n = 3384-3280 and 2231 cm-1 due
The reaction pathway for the formation of 6 can be
described as due to condensation of 5 with 1 accompanied
with elimination of a molecule of malononitrile to form in-
termediate 7, which reacted with another molecule of 1 to
give 6 (Fig. 1).
The condensation of 1 with o-phenylenediamine (8a)
was carried out to give acenaphtho[1,2-b]quinoxaline (9a)
and (Z)-2-(2-aminophenylamino)-2-(2-oxoacenaphthylen-
1(2H)-ylidene)acetonitrile (10a). Both structures can be
1
to absorption of NH, NH2 and CN, respectively, the H
NMR spectrum showed in addition to the aromatic protons,
three singlets at d = 7.21, 4.70 and 2.34 characteristic for
–NH, NH2 and CH3 protons, respectively. Further confir-
mation for 10b was established by the 13C NMR spectrum
which reveals two signals resonating at d = 21.3 and 116.9
corresponding to methyl and nitrile carbons, respectively
(see the Experimental Section).
1
deduced on the basis of their spectroscopic data. The H
NMR of 9a displayed five aromatic multiplets at d = 7.91-
7.96, 7.79-7.83, 7.65-7.71, 7.58-7.63 and 7.51-7.55 ppm,
each multiplet represents two aromatic protons. The 13
C
NMR spectrum revealed only ten carbon signals in the aro-
matic region, one signal resonated at d = 146.2 ppm distin-
guishing the (C=N) carbon group and the other carbon that
appeared at d = 142.8 ppm was characteristic for (N-C=C).
Moreover the four (CH) carbon atoms resonated at d =
Condensation of 1 with 5,6-diamino-pyrimidine-2,4-
diol hemisulphate (11) led to the formation of acenaphtho-
[1,2-g]pteridine-9,11-diol (12). Compound 12 exhibited IR
Fig. 1. Pathway describing the formation of 6.

1-(Dicyanomethylene)acenaphthene-2-one
J. Chin. Chem. Soc., Vol. 55, No. 5, 2008 1153
absorptions at n = 3512 and 1645 cm-1 which were ascrib-
able to OH and C=N, respectively. The 1H NMR spectrum
of this compound exhibited a singlet due to the OH proton
at d = 11.08 ppm along with resonances at d = 7.55-7.90
ppm as two doublets and one triplet for the aromatic pro-
tons. The 13C NMR spectrum of 12 displayed two distinct
resonances at d = 151.9 ppm (N-C(OH)-N) and 171.3 ppm
(N-C(OH)-C). Furthermore, the 13C NMR revealed two
signals at d = 144.7 ppm and 153.1 ppm corresponding to
the (C=N) groups. The MS with a molecular ion at m/z =
288 is in accordance with the assigned structure 12.
DMSO); d = 6.94-6.96 (2H, dd, J = 1.1, 7.7 Hz), 7.16 (2H,
t, J = 7.7 Hz), 7.58-7.62 (2H, m), 7.64-7.67 (2H, m), 7.73-
7.75 (2H, dd, J = 1.2, 7.2 Hz), 7.98-8.04 (2H, m); 13C NMR
(d6-DMSO); d = 112.2 (CH), 119.1 (CH), 122.5 (C), 122.8
(C), 127.2 (C), 127.4 (C), 128.2 (CH), 128.7 (C), 129.7
(CH), 131.3 (CH), 134.0 (CH), 136.1 (C), 162.6 (C=N);
MS (m/z) = 304 (M+ , 4), 302 [M+-2, 100], 288 (10), 276
[M+-N2, 66], 249 (22), 223 (8), 177 (6), 151 [1/2(M+-2),
100], 137 (62), 124 (46), 98 (20), 87 (12), 74 (22), 50 (10);
Anal. Calcd. for C22H12N2: C, 86.82; H, 3.97; N, 9.20.
Found: C, 86.63; H, 3.95; N, 9.01%.
(Z)-2-(8-aminonaphthalen-1-ylamino)-2-(2-oxoacenaph-
thylen-1(2H)-ylidene)acetonitrile (4)
EXPERIMENTAL SECTION
General procedures
Blue crystals (100 mg, 29%), mp > 340 °C. IR (KBr):
n = 3450-3368 (NH, NH2), 2220 (CºN), 1665 (C=O) cm-1;
1H NMR (d6-DMSO); d = 4.8 (2H, br-s, NH2), 7.22 (2H, d,
J = 9.1 Hz), 7.35 (1H, br s, 1NH), 7.71 (2H, d, J = 9.1 Hz),
7.82 (2H, t, J = 7.9 Hz), 8.54-8.58 (3H, dd, J = 1.0 Hz, J =
7.7 Hz), 9.25-9.29 (3H, dd, J = 1.1 Hz, J = 8.1 Hz); 13C
NMR (d6-DMSO); d = 103.6 (CH), 114.1 (C), 115.3 (C),
117.0 (CºN), 119.0 (CH), 119.9 (C), 121.7 (C), 125.8 (C),
126.5 (CH), 128.5 (C), 130.6 (C), 131.4 (CH), 131.8 (CH),
133.7 (CH), 175.0 (CO); MS (m/z) = 361 (M+, 8), 304 (12),
283 (20), 269 (50), 252 (4), 207 (4), 191 (40), 178 (20), 167
(100), 140 (10), 103 (2), 91 (50), 73 (60), 44 (80); Anal.
Calcd. for C24H15N3O: C, 79.76; H, 4.18; N, 11.63. Found:
C, 79.51; H, 4.03; N, 11.46.
Melting points are uncorrected. IR spectra were ob-
tained on a Nicolet 320 FT-IR using KBr pellets. 1H and 13C
NMR spectra were run at 400 and 100 MHz, respectively,
using a Bruker AM 400 Spectrometer with TMS as internal
standard. Mass spectra were run at 70 eV electron impact
mode using a Finnigan MAT 8430 spectrometer. For pre-
parative layer chromatography (plc), glass plates (20 ´ 48
cm) were covered with a slurry of silica gel Merck PF254
and air-dried, using the solvents listed for development.
Zones were detected by quenching of indicator fluores-
cence upon exposure to 254 nm UV light. Elemental analy-
ses were performed by the Microanalytical Unit at Assiut
University, Assiut, Egypt.
Starting Materials
(2Z,2¢Z)-2,2¢-(hydrazine-1,2-diylidene)diacenaphthylen-
1(2H)-one (6)
1,8-Diaminonaphthalene (2), o-phenylenediamine
(8a) and 3,4-diaminotoluene (8b) were bought from (Fluka),
whereas 5,6-diamino-pyrimidine-2,4-diol hemisulphate
(11) was bought from (Aldrich). 1-(Dicyanomethylene)-
acenaphthene-2-one (1) was prepared according to refer-
ence 21.
To a stirred solution of 1 (0.23 g, 1 mmol) in dry DMF
(25 mL) at room temperature, a solution of hydrazine hy-
drate (0.15 g, 3 mmol) dissolved in dry DMF (10 mL) was
added drop by drop for ten minutes. The reaction mixture
was heated under reflux conditions for 5 h, then cooled to
room temperature and left overnight, and the solvent was
concentrated in vacuo. The solid residue was recrystallized
from DMF/EtOH (1:1) to give pale yellow crystals 203 mg
(57%) of 6, m.p. 198-200 °C; IR (KBr): n = 3095 (CH),
1711 (C), 1640 (C=N) cm-1; 1H NMR (d6-DMSO); d = 7.45
(2H, s), 7.65-7.55 (4H, m), 7.75-7.71 (2H, dd, J = 1.2, 7.5
Reaction of 1-(dicyanomethylene)acenaphthene-2-one
(1) with 1,8-diaminonaphthalene (2)
To a stirred solution of 1 (0.23 g, 1 mmol) in dry DMF
(25 mL) at room temperature, a solution of 1,8-diamino-
naphthalene (2, 0.15 g, 1 mmol) was added drop by drop
for 10 minutes. The reaction mixture was heated under re-
flux conditions for 7 h, then cooled to room temperature
and left overnight; the solvent was concentrated in vacuo.
The residue was separated by plate chromatography to give
3 and 4 in 40 and 29% yield, respectively.
Hz), 7.89 (2H, d, J = 7.6 Hz), 8.16 (2H, d, J = 7.5 Hz); 13
C
NMR (d6-DMSO); d = 114.4 (CH), 121.8 (CH), 123.1
(CH), 125.9 (CH), 127.3 (CH), 127.6 (CH), 128.2 (C),
130.1 (C), 133.8 (C), 134.8 (C), 136.0 (C), 142.4 (CO); MS
(m/z) = 360 (M+, 4), 326 (40), 298 (6), 261 (4), 233 (16),
209 (80), 192 (6), 180 (M+/2, 24), 178 (40), 164 (100), 151
(80), 138 (46), 126 (20), 110 (8), 82 (22), 63 (24), 56 (12),
Acenaphtho[1,2-b]naphtho[1,8-ef][1,4]diazepine (3)
Black powder (122 mg, 40%), mp > 340 °C. IR
1
(KBr): n = 3105 (CH), 1624 (C=N) cm-1. H NMR (d6-

1154 J. Chin. Chem. Soc., Vol. 55, No. 5, 2008
El-Shaieb
28 (42); Anal. Calcd for C24H12N2O2: C, 79.99; H, 3.36; N,
7.77. Found: C, 79.67; H, 3.31; N, 7.61.
(23%); IR (KBr): n = 3268 (NH), 2181 (CºN), 1600 (C=N)
cm-1; 1H NMR (d6-DMSO); d = 4.6 (2H, br-s, NH2), 7.15
(1H, d, J = 9.1 Hz), 7.40 (1H, br, s, NH), 7.62-6.69 (2H, m),
7.86 (1H, t, J = 7.8 Hz), 7.92-7.95 (3H, m), 8.11-8.17 (3H,
m); 13C NMR (d6-DMSO); d = 112.7 (C), 115.3 (CN),
117.4 (CH), 121.2 (C), 123.8 (CH), 124.1 (CH), 125.4
(CH), 126.9 (C), 127.2 (CH), 128.3 (CH), 131.0 (C), 131.2
(CH), 133.7 (C), 135.3 (C), 138.6 (C), 141.2 (C), 164.6
(C=N); MS (m/z) = 311 [M+ , 42], 296 [M+-NH2, 80], 270
[M+-(HCN+NH2), 28], 204 (6), 190 (22), 166 (100), 148
(42), 124 (20), 110 (24), 96 (40), 70 (60); Anal. Calcd for
C20H13N3O: C, 77.16; H, 4.21; N, 13.50. Found: C, 76.94;
H, 4.07; N, 13.29%.
Reaction of 1 with o-phenylenediamine (8a) and 3,4-
diaminotoluene (8b)
To a stirred solution of 1 (0.23 g, 1 mmole) in dry
EtOH (20 mL) at room temperature, a solution of 1 mmole
of o-phenylenediamine (8a) and/or 3,4-diaminotoluene
(8b) dissolved in 10 mL dry EtOH was added drop by drop.
The reaction mixture was heated under reflux conditions
for 5 h. When the reaction mixture was cooled to room tem-
perature and left overnight, yellow crystals formed. The
crystals were filtered and recrystallized from EtOH to give
yellow needles of 9a and/or 9b. The filtrate was subjected
to plate chromatography using cyclohexane:ethylacetate
(5:3) as eluent to give blue crystals of 10a and/or 10b.
Acenaphtho[1,2-b]quinoxaline (9a)
(Z)-2-(2-amino-5-methylphenylamino)-2-(2-oxoace-
naphthylen-1(2H)-ylidene)acetonitrile (10b)
Blue crystals (95 mg, 31%), mp 200-202 °C. IR
(KBr): n = 3384-3280 (NH, NH2), 2231 (CºN), 1610
(C=N) cm-1; 1H NMR (d6-DMSO); d = 2.34 (3H, s, CH3),
4.7 (2H, br-s, NH2), 6.55 (1H, d, J = 1.3 Hz), 6.59-6.62
(1H, dd, J = 1.3 Hz, J = 7.5 Hz), 6.96 (1H, d, J = 7.5 Hz),
7.21 (1H, br-s, NH), 7.45-7.52 (3H, m), 7.79-7.84 (3H, m);
13C NMR (d6-DMSO); d = 21.3 (CH3), 116.9 (CN), 117.4
(CH), 123.8 (CH), 125.4 (CH), 126.9 (C), 128.3 (CH),
131.1 (CH), 131.3 (C), 133.7 (C), 135.5 (C), 136.4 (CH),
137.8 (CH), 138.1 (C), 138.6 (C), 164.2 (C=N); MS (m/z) =
325 [M+, 8], 292 [M+-(NH2 + CH3), 12], 267 [M+ - (NH2 +
CH3 + HCN), 44], 204 (6), 190 (22), 166 (100), 148 (42),
124 (20), 110 (24), 96 (40), 70 (60); Anal. Calcd. for
C21H15N3O: C, 77.52; H, 4.65; N, 12.91. Found: C, 77.28;
H, 4.54; N, 12.65.
Yellow crystals (EtOH), m.p. = 240 °C, 153 mg
(60%); IR (KBr): n = 1620 (C=N), 1590 (C=C) cm-1; 1H
NMR (DMSO); d = 7.91-7.96 (2H, m), 7.79-7.83 (2H, m),
7.65-7.71 (2H, m), 7.58-7.63 (2H, m), 7.51-7.55 (2H, m);
13C NMR (d6-DMSO); d = 123.7 (CH), 127.1 (CH), 127.4
(CH), 128.0 (C), 128.2 (C), 128.5 (C), 129.1 (CH), 129.6
(CH), 142.8 (N-C=C), 146.2 (C=N); MS (m/z) = 254 [M+,
100], 226 (30), 201 (6), 178 (44), 151 (40), 127 [M+/2, 50),
113 (10), 76 (20), 50 (26); Anal. Calcd for C18H10N2: C,
85.02; H, 3.96; N, 11.02. Found: C, 84.79; H, 4.01; N,
10.83%.
9-Methyl-acenaphtho[1,2-b]quinoxaline (9b)
Yellow needles (158 mg, 59%), mp 168-170 °C. IR
(KBr): n = 1630 (C=N), 1600 (C=C) cm-1; 1H NMR (d6-
DMSO); d = 2.61 (3H, s, CH3), 7.67-7.70 (1H, dd, J = 1.8
Hz, J = 8.4 Hz), 7.94 (2H, t, J = 8.1 Hz), 8.00 (1H, s), 8.10
(1H, d, J = 8.4 Hz), 8.29 (1H, d, J = 3.2 Hz), 8.31 (1H, d, J =
3.2 Hz), 8.40 (1H, d, J = 5.1 Hz), 8.42 (1H, d, J = 5.1 Hz);
13C NMR (d6-DMSO); d = 21.2 (CH3), 121.8 (CH), 121.9
(CH), 128.4 (CH), 128.9 (CH), 129.0 (CH), 129.3 (C),
129.6 (CH), 129.7 (CH), 129.8 (CH), 131.1 (CH), 131.2
(C), 131.5 (C), 135.3 (C), 139.2 (C),139.7 (C), 140.7 (C),
152.6 (C=N), 153.3 (C=N); MS (m/z) = 268 [M+, 100], 253
[M+-CH3, 22], 240 (64), 227 (12), 214 (20), 200 (6), 178
(48), 151 (40), 134 (80), 120 (40), 107 (20), 90 (100), 75
(18), 63 (40), 51 (16), 18 (12); Anal. Calcd for C19H12N2:
C, 85.05; H, 4.51; N, 10.44. Found: C, 84.83; H, 4.42; N,
10.27%.
Acenaphtho[1,2-g]pteridine-9,11-diol (12)
To a stirred solution of 1 (0.23 g, 1 mmole) in dry
DMF (25 mL) at room temperature, a solution of 4,5-di-
amino-pyrimidine-2,6-diol hemisulphate (11, 0.142 g, 1
mmol) dissolved in dry DMF (10 mL) was added drop by
drop for five minutes. The reaction mixture was heated un-
der reflux conditions for 9 h, then cooled to room tempera-
ture and left overnight. The solvent was concentrated in
vacuo. The solid residue was recrystallized from DMF/
EtOH (1:1) to give 185 mg (64%) of 12 as brown crystals
(DMF/EtOH), m.p. = 330-333 °C, IR (KBr): n = 3512
(OH), 1645 (C=N), 1591 (C=C); 1H NMR (d6-DMSO); d =
7.55 (2H, t, J = 3.2 Hz), 7.71 (2H, d, J = 7.6 Hz), 7.90 (2H,
d, J = 7.6 Hz), 11.08 (2H, s, 2OH); 13C NMR (d6-DMSO); d
= 122.8 (CH), 127.2 (CH), 127.5 (CH), 127.9 (C), 128.1
(C), 128.4 (C), 142.3 (C), 144.7 (C=N), 151.9 (N-C(OH)-
N), 153.1 (N-C-N), 171.3 (N-C(OH)-C); MS (m/z) = 288
(Z)-2-(2-aminophenylamino)-2-(2-oxoacenaphthylen-
1(2H)-ylidene)acetonitrile (10a)
Blue crystals (EtOH), m.p. = 189-192 °C, 68 mg

1-(Dicyanomethylene)acenaphthene-2-one
J. Chin. Chem. Soc., Vol. 55, No. 5, 2008 1155
[M+ , 20], 270 [M+-H2O, 6], 231 (22), 216 (18), 210 (26),
204 (40), 197 (60), 189 (20), 166 (24), 153 (100), 148 (46),
141 (4), 138 (18), 125 (100), 98 (10), 87 (42), 73 (60), 63
(30), 57 (24), 44 (80), 31 (44), 18 (100); Anal. Calcd. for
C16H8N4O2: C, 66.67; H, 2.80; N, 19.44. Found: C, 66.48;
H, 2.74; N, 19.29%.
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