Synthesis of Phenanthrene Derivatives through the Reaction of an α,α-Dicyanoolefin with α,β-Unsaturated Carbonyl Compounds

Article abstract of DOI:10.1002/hlca.201500120

Phenanthrene derivatives were prepared by reacting an α,α-dicyanoolefin with different α,β-unsaturated carbonyl compounds resulting from Wittig reaction of ninhydrin and phosphanylidene or condensation of barbituric acid and an aldehyde. The easy procedure, mild and metal-catalyst free, reaction conditions, good yields, and no need for chromatographic purifications are important features of this protocol. The structures of the product of type 3 and 5 were corroborated spectroscopically (IR, ¹H- and ¹³C-NMR, and EI-MS). A plausible mechanism for this type of reaction is proposed (Scheme 1).

Full text of DOI:10.1002/hlca.201500120

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Helvetica Chimica Acta – Vol. 98 (2015)
Synthesis of Phenanthrene Derivatives through the Reaction of an a,a-
Dicyanoolefin with a,b-Unsaturated Carbonyl Compounds
by Abdolali Alizadeh*, Seyed Yasub Hosseini, Hadi Sedighian, and Fahimeh Bayat
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
(phone: þ 98-21-88006631; fax: þ 98-21-88006544; e-mail: abdol_alizad@yahoo.com and
aalizadeh@Modares.ac.ir)
Phenanthrene derivatives were prepared by reacting an a,a-dicyanoolefin with different a,b-
unsaturated carbonyl compounds resulting from Wittig reaction of ninhydrin and phosphanylidene or
condensation of barbituric acid and an aldehyde. The easy procedure, mild and metal-catalyst free,
reaction conditions, good yields, and no need for chromatographic purifications are important features of
this protocol. The structures of the product of type 3 and 5 were corroborated spectroscopically (IR, 1H-
and 13C-NMR, and EI-MS). A plausible mechanism for this type of reaction is proposed (Scheme 1).
Introduction. – The interest for phenanthrene derivatives is connected with the
presence of their skeleton in a great number of natural products. They have been found
to exert a wide spectrum of biological activities, such as anti-HIV [1], anticancer [2],
antimycotic [3], antimalarial [4], and antiviral properties [5]. In addition, studies on
various substituted phenanthrene derivatives reveal that they exhibit tumor-inhibitory
potential [6], cytotoxicity [7], and anti-inflammatory properties [8]. Moreover,
phenanthrene derivatives are well known hydrocarbons found in crude oil [9], soil,
and sea sediments [10]. As a consequence, many approaches to this structure have been
disclosed in the literature. The traditional pathway is the Haworth synthesis, which
contains a series of steps including FriedelÀCrafts acylation, followed by a Clemmensen
reduction or WolffÀKishner reduction, cyclization, reduction, and dehydrogenation
[11]. Other reliable strategies to phenanthrenes are intramolecular condensations of
disubstituted biphenyls [12], photocyclization of stilbenes [13], Pd-catalyzed cycliza-
tion of arynes with alkynes [14], base-catalyzed ring transformation of 4-sec-amino-2-
oxo-5,6-dihydro-2H-benzo[h]chromene-3-carbonitriles [15], carbanion-induced ring
transformation of 2H-pyran-2-ones and 1-naphthalenone [16], and one-pot multi-
component reactions of aldehydes, malononitrile, 1-tetralone, and NH4OH [17]. Most
of these procedures suffer from the limitation of availability of precursors, low yields,
harsh reaction conditions, and low functional group tolerance.
The vinylogous addition, a variant of the Michael addition reaction [18], is a
technical strategy used for the formation of quaternary stereogenic centers [19],
spirocarbocycles [20], and polysubstituted benzene derivatives [21]. The high potential
of a,a-dicyanoolefins for generation of vinylogous carbanions has led them to readily
react with different electrophiles, such as 1,2-diaza-1,3-dienes [22], dialkyl acetylene-
dicarboxylates [23], aldehydes [24], ketones [25], nitrostyrenes [26], alkylidene
malonates [27], and imines [28].
ꢀ 2015 Verlag Helvetica Chimica Acta AG, Zürich

Helvetica Chimica Acta – Vol. 98 (2015)
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Results and Discussion. – The biological significance of the phenanthrene com-
pounds in mind and in continuation of our researches in the area of multicomponent
reaction using vinylogous Michael addition methodology [29], herein, we evaluate the
one pot reaction of 2-(3,4-dihydronaphthalen-1(2H)-ylidene)propanedinitrile [30]
(2), ninhydrin, and phosphanylidene. Our detailed study commenced with refluxing the
mixture of ninhydrin and phosphanylidene 1d in EtOH. Then, the mixture was cooled,
and 2-(3,4-dihydronaphthalen-1(2H)-ylidene)propanedinitrile and Et3N were added to
the mixture at room temperature. Monitoring by TLC revealed that the reactants were
consumed to yield a new product 3d. To establish optimal conditions, several solvents
and different bases were explored and the results showed that the reaction proceeded
with excellent yields in the presence of Et3N in EtOH (Table 1).
With the optimal conditions established, we turned our attention to investigate the
scope of this one-pot transformation by variation of the phosphanylidene component
(Table 2). It is noticeable that, interpretation of 1H-NMR and 13C-NMR spectra
indicates that product 3’a is obtained as the imino tautomeric form, while product
3b – 3d are obtained as the amino tautomer.
As part of our ongoing studies on the development of vinylogous addition of a,a-
dicyanoolefins, we next found that 2-(3,4-dihydronaphthalen-1(2H)-ylidene)propane-
dinitrile 2 can react with the Knoevenagel product 4 of an aromatic aldehyde and
barbituric acid in the presence of Et3N, leading to phenanthrene derivatives 5. Initially,
5-(arylmethylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-triones were prepared ac-
cording to the literature [31]. The best results for the preparation of 5b were obtained
by performing the reaction in EtOH in the presence of Et3N (Table 3).
In the next step, we examined the scope of this transformation by variation of the
substituent in the aldehyde (Table 4). All the products were obtained in good yields.
Table 1. Results of the Synthesis of 3d under Different Reaction Conditions
Entry
Solvent
Base
Yield [%]
Time [h]
1
2
3
4
5
6
7
8
9
EtOH
EtOH
EtOH
MeOH
MeOH
CH2Cl2
CH2Cl2
MeCN
MeCN
THF
Et3N
78
68
65
73
64
50
45
72
55
50
45
8
8
8
Na2CO3
NaOH
Et3N
Na2CO3
Et3N
Na2CO3
Et3N
Na2CO3
Et3N
10
10
10
10
10
10
12
12
10
11
THF
Na2CO3

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Table 2. Synthesis of Phenanthrenes 3a – 3d
Entry
R1
Product
Yield [%]
1
2
3
4
H
Br
Cl
MeO
3’a
3b
3c
65
71
74
67
3d
Table 3. Results of the Synthesis of 5b under Different Reaction Conditions
Entry
Solvent
Base
Yield [%]
Time [h]
1
2
3
4
5
6
7
8
9
EtOH
EtOH
EtOH
MeOH
MeOH
CH2Cl2
CH2Cl2
MeCN
MeCN
THF
Et3N
84
72
60
78
68
60
55
76
63
55
40
1
1
1
2
2
2
2
2
2
2
2
Na2CO3
NaOH
Et3N
Na2CO3
Et3N
Na2CO3
Et3N
Na2CO3
Et3N
10
11
THF
Na2CO3

Helvetica Chimica Acta – Vol. 98 (2015)
Table 4. Synthesis of Phenanthrenes 5a – 5d
1429
Entry
R2
Product
Yield [%]
1
2
3
4
3-Br
4-Cl
3-MeO
3-NO2
5a
5b
5c
5d
82
86
85
83
1
All characterization including mass spectrometric analyses, IR, H-NMR, and
13C-NMR proved the structures of the products 3a – 3d and 5a – 5d. For example, the
MS of 3d displayed the molecular ion peak at m/z 486, which is in agreement with the
proposed structure. In the IR spectrum of 3d, two absorption bands at 3437 and
3250 cmÀ1, a sharp band at 2215 cmÀ1, and absorption bands at 1710, 1659, 1588, and
1109 cmÀ1 attributed to NH2, CN, C¼O, C¼C, and CÀO stretching frequencies
respectively, indicating the most significant functional groups of the product. The
1H-NMR spectrum of 3d exhibited two multiplets for two CH2 groups at d(H) 1.82 –
1.89 and 2.55 – 2.67. Three singlet signals for MeO, CH, and NH2 appeared at d(H)
3.86, 5.67, and 6.92, respectively, and twelve aromatic H-atoms gave rise to character-
istic signals in the aromatic region of the spectrum. Observation of 29 distinct signals in
1
the H-decoupled 13C-NMR spectrum of 3d is also in agreement with the proposed
structure.
In the IR spectrum of 5c, absorption bands at 3419 and 3237, at 2216, and at
1750 cmÀ1, attributed to NH2, C ꢀ N, and C¼O stretching frequencies respectively,
indicated the most significant functional groups of the product. The 1H-NMR spectrum
of 5a showed three multiplet signals at d(H) 1.70 – 1.73, 1.84 – 1.93, and 2.46 – 2.55
attributed to two CH2 groups. Five singlet signals at d(H) 2.91, 2.97, 3.69, 4.48, and 6.98
were ascribed to two MeN and one MeO, CH, and NH2 groups, respectively. Eight H-
atoms of aryl groups appeared in the aromatic region of spectrum. Observation of 26
distinct signals in the 1H-decoupled 13C-NMR spectrum of 5c is in agreement with the
proposed structure.
Based on these results, a plausible mechanism for the formation of the
phenanthrene derivatives 3 and 5 has been proposed (Scheme). Deportation of a,a-
dicyanoolefin 2 with Et3N furnishes the vinylogous carbanion 7 which attacks the a,b-
unsaturated compounds 6 resulting from Wittig reaction, or 4, followed by an
intramolecular nucleophilic addition on the CN group (8 ! 9 and 10 ! 11) and
protonation (9 ! 3’ and 11 ! 12). By a 1,5-H shift, the imines 3’ and 12 are converted to
the corresponding products 3 and 5.

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Helvetica Chimica Acta – Vol. 98 (2015)
Scheme. Mechanistic Rationalization for the Formation of 3 and 5

Helvetica Chimica Acta – Vol. 98 (2015)
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To sum up, we have developed a highly convergent one-pot domino protocol for the
synthesis of phenanthrene derivatives by using readily available precursors. Other
significant advantages of this method include operational simplicity, good yields of
products, and that no ligands, acidic medium, metal catalysts, and column chromatog-
raphy are required.
Financial support of this research from Tarbiat Modares University, Iran, is gratefully acknowledged.
Experimental Part
General. M.p.: Electrothermal 9100. IR Spectra: NICOLET FT-IR 100 spectrometer, KBr pellets; n˜
.
in cmÀ1 1H-NMR (300 and 400 MHz) and 13C-NMR (75 and 100 MHz) spectra: Bruker DRX-400
AVANCE and Bruker DRX-500 AVANCE spectrometers; d in ppm rel. to Me4Si as internal standard, J in
Hz. MS: FINNIGAN-MATT 8430 mass spectrometer operating at an ionization potential of 70 eV; in m/
z. Elemental analyses: Heraeus CHNÀOÀRapid analyzer; in %.
General Procedure 1 (for 3). A mixture of ninhydrine (1 mmol) and phosphorane 1 (1 mmol) in
EtOH (3 ml) was stirred for 30 min at reflux temp. Then, 2-(3,4-dihydronaphthalen-1(2H)-ylidene)-
propanedinitrile [30] (2; 1 mmol) and Et3N (1 mmol) was added to it, and the mixture was stirred at r.t.
After completion, monitored by TLC, the mixture was filtered, and the precipitate was washed with
EtOH (2 Â 4 ml) to afford the pure product 2.
General Procedure 2 (for 5). Et3N (1 mmol) was added to a soln. of 5-(arylmethylene)-1,3-
dimethylpyrimidine-2,4,6(1H,3H,5H)-triones 3 (1 mmol) and 2 (1 mmol), and the mixture was stirred at
r.t. After completion of the reaction, monitored by TLC, the mixture was filtered, and the precipitate was
washed with EtOH (2 Â 4 ml) to afford the pure product 5a – 5d.
1’-Benzoyl-1,3,3’,9’,10’,10’a-hexahydro-3’-imino-1,3-dioxo-spiro[2H-indene-2,2’(1’H)-phenanthrene]-
4’-carbonitrile (3’a). Yield: 0.30 g (65%). White powder. M.p. 198 – 2008. IR: 3226 (NH), 2198 (CN),
1
1709 (C¼O), 1653 (C¼O), 1550, 1478 (Ar). H-NMR (300.0 MHz, (D6)DMSO): 1.18 – 1.85 (m, 2 H);
3
3
1.87 – 2.06 (m, 2 H); 2.76 – 2.94 (m, 1 H); 3.47 – 3.40 (m, 1 H); 5.08 (d, J ¼ 9.5, 1 H); 7.29 (d, J ¼ 4.9,
1 H); 7.35 – 7.44 (m, 1 H); 7.46 – 7.62 (m, 3 H); 7.66 – 7.75 (m, 1 H); 7.86 – 8.13 (m, 5 H); 8.18 (d, 3J ¼ 6.7,
1 H); 10.34 (s, 1 H). 13C-NMR (100.0 MHz, (D6)DMSO): 27.5; 29.0; 49.1; 61.7; 71.2; 103.2; 115.8; 123.0;
123.9; 126.3; 128.6; 129.0; 129.3; 129.5; 130.0; 133.0; 134.7; 136.2; 136.5; 136.6; 141.0; 141.6; 142.4; 164.5;
165.2; 195.0; 198.6; 200.7. EI-MS (70 eV): 456 (4, Mþ), 438 (2), 413 (44), 394 (13), 351 (89), 333 (47), 306
(13), 292 (9), 267 (41), 252 (13), 239 (18), 226 (8), 203 (9), 190 (13), 165 (9), 152 (8), 133 (9), 105 (100),
91 (8), 77 (95), 51 (8). Anal. calc. for C30H20N2O3 (456.50): C 78.93, H 4.42, N 6.14; found: C 78.86, H
4.36, N 6.07.
3’-Amino-1’-(4-bromobenzoyl)-1,3,9’,10’-tetrahydro-1,3-dioxo-1’H-spiro[indene-2,2’-phenanthrene]-
4’-carbonitrile (3b). Yield: 0.38 g (71%). Green powder. M.p. 217 – 2198 (dec.). IR: 3432, 3249 (NH2),
2216 (CN), 1708 (C¼O), 1671 (C¼O), 1588, 1454 (Ar). 1H-NMR (400 MHz, (D6)DMSO): 1.78 – 1.89 (m,
2 H); 2.53 – 2.67 (m, 2 H); 5.64 (s, 1 H); 6.97 (s, 2 H); 7.18 (t, 3J ¼ 10.0, 1 H); 7.19 (d, 3J ¼ 12.0, 1 H); 7.30
(t, 3J ¼ 7.4, 1 H); 7.41 (dd, 3J ¼ 8.0, 1 H); 7.61 (d, 3J ¼ 7.6, 1 H); 7.75 (d, 3J ¼ 8.0, 1 H); 7.80 (d, 3J ¼ 7.6, 1 H);
7.89 (d, 3J ¼ 7.6, 1 H); 7.96 (d, 3J ¼ 8.0, 1 H); 8.00 – 8.06 (m, 3 H). 13C-NMR (100 MHz, (D6)DMSO): 25.9;
27.8; 53.3; 59.7; 74.9; 120.8; 123.1; 123.7; 124.2; 126.1; 126.8; 126.9; 127.3; 129.0; 130.7; 131.1; 132.2; 132.3;
135.3; 135.6; 136.0; 136.9; 141.9; 141.9; 157.3; 194.8; 197.6; 198.3. EI-MS (70 eV): 534 (1, Mþ), 491 (1), 394
(1), 351 (100), 333 (30), 306 (7), 277 (10), 256 (6), 239 (3), 203 (6), 185 (50), 166 (26), 152 (18), 129 (32),
97 (16), 69 (67), 55 (25). Anal. calc. for C30H19BrN2O3 (535.39): C 67.30, H 3.58, N 5.23; found: C 67.22, H
3.40, N, 5.18.
3’-Amino-1’-(4-chlorobenzoyl)-1,3,9’,10’-tetrahydro-1,3-dioxo-1’H-spiro[indene-2,2’-phenanthrene]-
4’-carbonitrile (3c). Yield: 0.37 g (74%). Green powder. M.p. 190 – 1938. IR: 3438, 3248 (NH2), 2207
(CN), 1712 (C¼O), 1671 (C¼O), 1605, 1504 (Ar). 1H-NMR (400 MHz, (D6)DMSO): 1.78 – 1.87 (m,
2 H); 2.51 – 2.63 (m, 2 H); 5.56 (s, 1 H); 6.97 (s, 2 H); 7.18 (t, 3J ¼ 10.0, 1 H); 7.19 (t, 3J ¼ 11.6, 1 H); 7.30 (t,
3
3
3J ¼ 7.2, 1 H); 7.61 (d, J ¼ 7.2, 4 H); 7.77 (d, J ¼ 7.2, 1 H); 7.88 (t, 3J ¼ 7.6, 1 H); 7.93 – 8.02 (m, 3 H).
13C-NMR (100 MHz, (D6)DMSO): 25.9; 27.8; 53.4; 59.7; 74.9; 120.9; 123.1; 123.7; 124.2; 126.1; 126.8;

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Helvetica Chimica Acta – Vol. 98 (2015)
127.3; 128.7; 129.4; 130.8; 130.8; 131.9; 135.0; 135.6; 136.0; 136.9; 139.6; 141.9; 141.9; 157.3; 194.8; 197.4;
198.3. EI-MS (70 eV): 491 (9, Mþ), 410 (3), 394 (6), 347 (13), 305 (6), 277 (46), 239 (32), 202 (26), 183
(100), 157 (42), 139 (26), 104 (98), 76 (81), 50 (13). Anal. calc. for C30H19ClN2O3 (490.94): C 73.40, H
3.90, N 5.71; found: C 73.32, H 3.83, N 5.65.
3’-Amino-1,3,9’,10’-tetrahydro-1’-(4-methoxybenzoyl)-1,3-dioxo-1’H-spiro[indene-2,2’-phenan-
threne]-4’-carbonitrile (3d). Yield: 0.34 g (68%). Gray powder. M.p. 227 – 2308 (dec.). IR: 3437, 3250
(NH2), 2215 (CN), 1710 (C¼O), 1659 (C¼O), 1588, 1403 (Ar), 1109 (CÀO). 1H-NMR (400.1 MHz,
(D6)DMSO): 1.82 – 1.89 (m, 2 H); 2.55 – 2.67 (m, 2 H); 3.86 (s, 3 H); 5.67 (s, 1 H); 6.92 (s, 2 H); 7.04 (d,
3J ¼ 8.8, 2 H); 7.20 (t, 3J ¼ 9.6, 2 H); 7.29 (t, 3J ¼ 7.4, 1 H); 7.60 (d, 3J ¼ 7.6, 1 H); 7.85 (d, J ¼ 7.2, 1 H); 7.93
(d, 3J ¼ 8, 4 H); 7.98 – 8.04 (m, 1 H). 13C-NMR (100 MHz, (D6)DMSO): 25.6; 27.8; 53.6; 55.7; 59.6; 75.00;
114.4; 119.3; 121.6; 122.9; 123.6; 124.1; 126.1; 126.5; 126.7; 127.3; 129.3; 131.4; 131.9; 135.3; 136.0; 136.8;
142.0; 142.1; 157.4; 164.1; 194.8; 196.4; 198.9. EI-MS (70 eV): 486 (1, Mþ), 443 (16), 425 (1), 399 (3), 351
(18), 335 (13), 297 (27), 277 (21), 264 (21), 239 (18), 226 (18), 190 (86), 176 (21), 152 (30), 135 (100), 121
(17), 104 (53), 77 (57), 63 (10), 50 (6). Anal. calc. for C31H22N2O4 (486.52): C 76.53, H 4.56, N 5.76;
found: C 76.45, H 4.48, N 5.69.
3-Amino-1-(3-bromophenyl)-1’,3’,4’,6’,9,10-hexahydro-1’,3’-dimethyl-2’,4’,6’-trioxo-1H,2’H-spiro[-
phenanthrene-2,5’-pyrimidine]-4-carbonitrile (5a). Yield: 0.43 g (82%). White powder. M.p. 190 – 1938.
1
IR: 3417, 3209 (NH2), 2209 (CN), 1748 (C¼O), 1677 (NCON), 1596, 1437 (Ar). H-NMR (400 MHz,
(D6)DMSO): 1.72 – 1.87 (m, 2 H); 2.42 – 2.57 (m, 2 H); 2.93 (s, 3 H); 3.02 (s, 3 H); 4.50 (s, 1 H); 6.99 (s,
3
3
3
2 H); 7.07 (d, J ¼ 8.0, 1 H); 7.17 – 7.31 (m, 5 H); 7.52 (d, J ¼ 8.0, 1 H); 7.64 (d, J ¼ 7.6, 1 H). 13C-NMR
(100 MHz, (D6)DMSO): 26.8; 28.2; 28.6; 28.6; 55.1; 61.8; 76.3; 119.4; 121.3; 122.6; 123.7; 125.6; 126.0;
126.9; 127.2; 128.3; 130.4; 131.2; 131.9; 132.1; 136.4; 138.3; 149.9; 155.2; 165.1; 167.5. EI-MS (70 eV): 518
(1, Mþ), 498 (1), 437 (1), 362 (12), 334 (4), 321 (64), 307 (4), 281 (37), 266 (29), 243 (26), 226 (4), 209
(21), 194 (91), 180 (24), 166 (40), 152 (23), 129 (100), 116 (35), 101 (52), 75 (40), 56 (35). Anal. calc. for
C26H21BrN4O3 (517.38): C 60.36, H 4.09, N 10.83; found: C 60.27, H 3.99, N 10.79.
3-Amino-1-(4-chlorophenyl)-1’,3’,4’,6’,9,10-hexahydro-1’,3’-dimethyl-2’,4’,6’-trioxo-1H,2’H-spiro[-
phenanthrene-2,5’-pyrimidine]-4-carbonitrile (5b). Yield: 0.41 g (86%). White powder. M.p. 204 – 2058.
1
IR: 3425, 3252 (NH2), 2212 (CN), 1751 (C¼O), 1680 (NCON), 1598, 1441 (Ar). H-NMR (400 MHz,
(D6)DMSO): 1.72 – 1.83 (m, 2 H); 2.43 – 2.54 (m, 2 H); 2.91 (s, 3 H); 3.02 (s, 3 H); 4.47 (s, 1 H); 6.95 (s,
2 H); 7.07 (d, 3J ¼ 8.4, 1 H); 7.16 – 7.21 (m, 2 H); 7.29 (td, 3J ¼ 7.6, 2J ¼ 2.0, 1 H); 7.37 (d, 3J ¼ 8.4, 2 H); 7.63
(d, 3J ¼ 7.6, 1 H). 13C-NMR (100 MHz, (D6)DMSO): 26.8; 28.2; 28.6; 55.0; 61.7; 76.4; 119.4; 123.0; 124.0;
125.4; 126.0; 126.8; 127.2; 128.2; 131.12; 132.2; 132.9; 134.7; 136.4; 149.9; 155.2; 165.1; 167.5. EI-MS
(70 eV): 472 (3, Mþ), 455 (1), 361 (9), 316 (5), 290 (4), 277 (54), 254 (8), 220 (20), 205 (8), 183 (85), 165
(90), 152 (36), 129 (100), 115 (32), 101 (32), 75 (22), 58 (20). Anal. calc. for C26H21ClN4O3 (472.93): C
66.03, H 4.48, N 11.85; found: C 65.92, H 4.39, N 11.78.
3-Amino-1’,3’,4’,6’,9,10-hexahydro-1-(3-methoxyphenyl)-1’,3’-dimethyl-2’,4’,6’-trioxo-1H,2’H-spiro[-
phenanthrene-2,5’-pyrimidine]-4-carbonitrile (5c). Yield: 0.39 g (85%). White powder. M.p. 234 – 2378.
IR: 3419, 3237 (NH2), 2216 (CN), 1750 (C¼O), 1683 (NCON), 1591, 1443 (Ar). 13H-NMR (400 MHz,
(D6)DMSO): 1.70 – 1.73 (m, 2 H); 1.84 – 1.93 (m, 2 H); 2.46 – 2.55 (m, 2 H); 2.91 (s, 3 H); 2.97 (s, 3 H);
3.69 (s, 3 H); 4.48 (s, 1 H); 6.54 (s, 1 H); 6.57 (d, 3J ¼ 8.0, 1 H); 6.88 (d, 3J ¼ 7.6, 1 H); 6.98 (s, 2 H); 7.18 –
7.23 (m, 3 H); 7.29 (t, 3J ¼ 7.6, 1 H); 7.62 (d, 3J ¼ 7.6, 1 H, CH of Ar). 13C-NMR (100 MHz, (D6)DMSO):
26.9; 28.2; 28.5; 28.7; 55.0; 56.5; 61.9; 76.4; 113.8; 114.7; 119.5; 121.5; 123.0; 123.8; 125.4; 125.9; 126.7;
127.1; 129.3; 132.3; 136.5; 136.6; 149.8; 155.6; 159.0; 165.1; 168.2. EI-MS (70 eV): 468 (11, Mþ), 451 (8),
424 (1), 410 (1), 392 (1), 361 (14), 337 (4), 312 (12), 286 (35), 273 (81), 259 (12), 243 (21), 216 (44), 194
(72), 183 (45), 166 (42), 152 (24), 129 (100), 116 (36), 102 (38), 89 (38), 63 (26), 51 (14). Anal. calc. for
C27H24N4O4 (468.51): C 69.22, H 5.16, N 11.96; found: C 69.13, H 5.06, N 11.86.
3-Amino-1’,3’,4’,6’,9,10-hexahydro-1’,3’-dimethyl-1-(3-nitrophenyl)-2’,4’,6’-trioxo-1H,2’H-spiro[phe-
nanthrene-2,5’-pyrimidine]-4-carbonitrile (5d). Yield: 0.48 g (83%). White powder. M.p. 249 – 2518. IR:
3419, 3267 (NH2), 2210 (CN), 1747 (C¼O), 1682 (NCON), 1597, 1436 (Ar). 1H-NMR (400 MHz,
(D6)DMSO): 1.78 – 1.87 (m, 2 H); 2.37 – 2.56 (m, 2 H); 2.90 (s, 3 H); 3.08 (s, 3 H); 4.66 (s, 1 H); 6.70 (s,
2 H); 7.18 (t, 3J ¼ 5.6, 1 H); 7.22 (d, 3J ¼ 7.6, 1 H); 7.31 (t, 3J ¼ 8.8, 1 H); 7.61 – 7.65 (m, 2 H); 7.68 (d, 3J ¼
7.6, 1 H); 8.03 (s, 1 H); 8.18 (d, 3J ¼ 6.4, 1 H). 13C-NMR (100 MHz, (D6)DMSO): 26.8; 28.3; 28.6; 28.8;
53.5; 61.5; 76.2; 119.4; 122.9; 123.3; 123.9; 123.9; 125.6; 126.0; 127.0; 127.3; 129.9; 131.9; 136.0; 136.4;

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138.8; 147.4; 150.1; 155.0; 165.3; 166.7. EI-MS (70 eV): 483 (1, Mþ), 466 (6), 448 (3), 419 (2), 381 (1), 352
(4), 327 (8), 310 (5), 288 (75), 272 (66), 242 (66), 215 (21), 194 (89), 179 (25), 166 (41), 147 (25), 129
(100), 116 (37), 101 (47), 75 (44), 56 (39). Anal. calc. for C26H21N5O5 (483.48): C 64.59, H 4.38, N 14.49;
found: C 64.30, H 4.29, N 14.39.
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Received Mai 16, 2015