Synthesis of spiro(indenepyrazole) and indenotriazinone derivatives from 4-substituted thiosemicarbazides and (1,3-dioxo-2,3-dihydro-1H-inden-2- ylidene)propanedinitrile

Article abstract of DOI:10.3184/030823410X12810986062376

In a multistep reaction, N-substituted-5'-amino-4'-cyano-1,3-dioxo-1,3- dihydro-spiro[indene-2,3'-pyrazole]-2'(1H) carbothioamides (63-71 %) and 4-substituted-3-thioxo-3/y-indeno[1,2-e][1,2,4] triazin-9(4/H)-ones (17-26 %) have been formed, from a series of 4-substituted thiosemicarbazides 1a-f with (1,3-dioxo-2,3-dihydro-1H-inden- 2-ylidene)propanedinitrile 3 in aerated ethyl acetate. Rationales of these conversions involving the nucleophilic reactions and condensation are presented.

Full text of DOI:10.3184/030823410X12810986062376

JOURNAL OF CHEMICAL RESEARCH 2010
RESEARCH PAPER 493
SEPTEMBER, 493–497
Synthesis of spiro(indenepyrazole) and indenotriazinone derivatives from
4-substituted thiosemicarbazides and (1,3-dioxo-2,3-dihydro-1H-inden-2-
ylidene)propanedinitrile
Alaa A. Hassana*, Ahmed M. Nour El.Dina, Fathy F. Abdel Latifa, Sara M. Mostafaa and
Stefan Bräseb
aChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt
bInstitute of Organic Chemistry, Karlsruhe Institute ofTechnology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
In a multistep reaction, N-substituted-5′-amino-4′-cyano-1,3-dioxo-1,3-dihydro-spiro[indene-2,3′-pyrazole]-2′(1H)
carbothioamides (63–71 %) and 4-substituted-3-thioxo-3H-indeno[1,2-e][1,2,4] triazin-9(4H)-ones (17–26 %) have
been formed, from a series of 4-substituted thiosemicarbazides 1a–f with (1,3-dioxo-2,3-dihydro-1H-inden-
2-ylidene)propanedinitrile 3 in aerated ethyl acetate. Rationales of these conversions involving the nucleophilic
reactions and condensation are presented.
Keywords: 4-substituted thiosemicarbazides, spiro(indenepyrazoles), indenotriazines
(1,3-Dioxo-2,3-dihydro-1H-inden-2-ylidene)propanedini-
trile 3 may be considered to be analogous to ethenetetracar-
bonitrile (2,TCNE) in its reactions (Fig. 1). Like the latter it
readily adds N-nucleophiles such as secondary aliphatic19,20
and primary aromatic amines at the dicyanomethylene carbon
Finding new methodologies for the synthesis of a family of
biologically potent compounds by employing building blocks
with multi-functional groups is a key issue for drug discov-
ery.1–6 Thiosemicarbazides 1 appear to be ideal candidates for
the development of such processes, since they are the core fea-
ture in families of compounds known to display biological
activities, e.g. pyrazoles,7 1,2,4-triazoles,7–9 1,3,4-oxadiazoles,8
1,3,4-thiadiazoles,7 1,3-thiazoles,10 1,2,4-triazepines,11 1,3,4-
thiadiazines 12 and 1,3,4-thiadiazepines.13
Four-, five-, six- and seven-membered heterocyclic com-
pounds were prepared by reaction of thiosemicarbazide
derivatives with α- and β- haloketones.14–16 The N2 of thio-
semicarbazide group is a softer nucleophilic centre than the
harder and more powerful terminal nitrogen N1. Thus, reagents
susceptible to nucleophilic attack by N1 may in a second
step undergo cyclisation to give heterocycles even under mild
reaction conditions.14,15
It has been reported that, 4-substituted thiosemicarbazides 1
reacted with ethenetetracarbonitrle (2,TCNE) to give pyrazole,
thiadiazepine and pyrazolothiadiazole derivatives.17 On the
other hand, the reaction of 4-substituted thiosemicarbazides
with (2,4,7-trinitro-4H-fluoren-9-ylidene)propanedinitrile in
pyridine to form spiro[fluorene-9,3′-triazole] derivatives have
been reported.18
Fig. 1
Scheme 1
* Correspondent. E-mail: alaahassan2001@yahoo.com

494 JOURNAL OF CHEMICAL RESEARCH 2010
Scheme 2
atom with release of hydrogen cyanide analogously to the
corresponding reactions of TCNE.21–23 Recently we reported
an efficient transformation of aldehyde thiosemicarbazides
7a–f showed IR absorption peaks at υ (cm−1) = 3430–3150
(NH2 and NH), 2220–2210 (CN) and carbonyl absorption at
1755–1735 as expected for indane-1,3-dione ring system,
1575–1565 (NH def. and C–N str.), 1365-1350, 1010–980
cm-1(C=S and C–N). The mass spectra (EI mode) of com-
pounds 7a–f were characterised by molecular ions of low
intensity and loss of 27 a.m.u (representing HCN) and 66 a.
m.u (representing NC–C=C–NH2). The resulting fragment
ions undergo loss of 28 a.m.u. (dinitrogen or CO). Also, the
mass spectra exhibited the loss of R–N=C=S and C6H4–CO
4a–e with
3 into indeno[2,1-e][1,3,4]oxadiazine-9-ones
5a–e and 4-oxoindeno[1,2-c] pyrazole-3-carbonitriles 6a–e
(Scheme 1).24
These intriguing transformations led us to investigate the
reactions of 4-substituted thiosemicarbazides 1a–f with 3. The
latter compound offer C/C multiple bonds and the electrophilic
carbonyl and nitrile carbon atoms for attack by nucleophiles
and compounds 1a–f may react at least with N1, N2 and sulfur
atoms as nucleophilic sites. Thus several options for interac-
tion between 1a–f and 3 may be envisaged, as will be outlined
later. We chose thiosemicarbazides 1a–f having aryl groups
(unsubstituted benzene and aryl groups with electron with-
drawing substituents on the benzene ring) as well as alkyl
groups, in order to examine their effect on the course of the
reaction.
1
fragments. The H NMR spectrum of 7a showed three broad
signals at 6.97, 9.85 and 10.95 with the integration ratio 2:1:1
attributed to NH2, NH attached to phenyl and pyrazole-NH,
besides the aromatic protons. Distinctive signals appeared in
the 13C NMR spectrum of 7a at δ = 194.56, 193.13 (C-1,3),
186.01 (C=S), 119.45 (CN), 106.76 (spiro-C-2,3′), pyrazole-
C-4′ and C-5′ resonate at 59.73 and 174.68 ppm, respectively
are in accordance with the observed trends in the δ values
for C-atoms in Push–Pull alkenes.25,26 The analytical data of
7 would also match other isomers of product 9–12 (Figs 2
and 3).
Results and discussion
Solutions of 3 and substituted thiosemicarbazides 1a–f in ethyl
acetate in a molar ratio of 1:1 were refluxed. Concentration
of the reaction mixture yielded a reddish brown crystals from
N-substituted-5′-amino-4′-cyano-1,3-dioxo-1,3-dihydrospiro
[indene-2,3′-pyrazole]-2′(1′H)- carbothioamide 7a–f (63–
71 %). The remaining soluble materials were subjected to
preparative layer chromatography to give 4-substituted-3-
thioxo-3H-indeno[1,2-e]triazine-9(4H)-one 8a–e (17–26 %).
The structure of compounds 7a–f and 8a–e were assigned
using spectroscopic tools such as IR, NMR (1H, 13C) and mass
spectrometry, in addition to elemental analyses. Compounds
The alternative structures 10–12 could be ruled out on the
1
basis of H and 13C NMR. Therefore, we will concentrate on
the interplay between the formation of the products 7a–f and
the alternative structure 9 (Fig. 2). The a priori possible iso-
meric structures 9 were ruled on the basis of 1H NMR, because
in compounds 9, the pyrazole-NH is isolated and not adjacent
to C=C double bond and therefore, the δ value must be consid-
erably lower. A value which should be expected for structure 9
is 4.5 ppm as given in the literature.27 On the other hand, the
1H- NMR spectrum of 7a shows the presence of pyrazole-NH
at (δH= 10.95 ppm) due to cojungation with π-system. Further-
more, in the 13C NMR of 7a–f, the pyrazole-C-5′ is regularly
downfield shifted [7a (C-5′ = 174.68), 7b (C-5′ = 173.66), 7c
(C-5′ = 170.31), 7d (C-5′ = 173.65), 7e (C-5′ = 173.54), 7f (C-
5′ = 172.82) compared to pyrazole-C-3′ in compounds 9 (which
has been resonated with range 158.45–158.64).28
The IR spectra of 8a–e showed strong absorption signals
between 1720 and 1705 cm−1 for the carbonyl group, and
between 1370 and 1355 cm−1 as well as 1010 and 995 cm−1 to
strong vibration coupling of C=S and C–N entities.
1
The H NMR spectrum of 8c showed signals at 7.80–8.20
due to aryl protons of indanedione. The 1H NMR of 8c clearly
indicated the presence of allyl group which appeared as three
multiplets centred at 4.30, 5.20–5.30 and 5.85–5.92 ppm due
to allyl-CH2N, allyl-CH2= and allyl-CH= respectively. The
Fig. 2

JOURNAL OF CHEMICAL RESEARCH 2010 495
Fig. 3
presence of allyl group also evident from the 13C-DEPT-NMR
spectrum exhibiting positive signals at δ = 136.34 (allyl-CH=)
and negative signals at 47.36 and 116.96 due to allyl-CH2N
and allyl-CH2= respectively. Further peaks at 193.01 (CO) and
185.85 which clearly support a C=S group and not an isothio-
urea carbon as in 13.
The gross formula C13H9N3OS of 8c was confirmed by the
mass spectrum, which exhibited the molecular ion at m/z 255
(14%). The fragmentation patterns of the mass spectra of 8
characterised by the loss of R–N=C=S and (N2 or CO) giving
rise to the ion m/z 128 common in the spectra of all compounds
8a–e.
The formation of 7 and 8 indicate that thiosemicarbazides
1a–f react with 3 through a nucleophilic attack of 1a–f to the
C≡N triple bond of 3 to form the intermediate 14, compound
14 exerts its nucleophilic character and intramolecular nucleo-
philic attack of NH to the C=C douple bond, where the elec-
tron-withdrawing groups (two carbonyl and one nitrile groups)
facilitate this reaction to form the product 7a–f. On the other
hand, nucleophilic attack of 1a–f to C=C double bond of 3 and
elimination a molecule of malononitrile afforded the formation
of intermediate 15. Nucleophilic attack of NH to the carbonyl
group followed by elimination H2O gave thioxoidenotriazines
8a–e.
4-Substituted thiosemicarbazides 1a–f were synthesised by the
reaction of hydrazine hydrate with the appropriate isothiocyanate
according to the literature: 4-phenyl- thiosemicarbazide (1a),29,30 4-
benzylthiosemicarbazide (1b),30,31 4-allylthiosemicarbazides (1c),31,32
4-(4-fluorophenyl)thiosemicarbazide (1d),33 4-(3,5-difluorophenyl)th
iosemicarbazide (1e)34 and 4-[4(trifluoromethyl)phenyl] thiosemicar-
bazide (1f).34
2-(1,3-Dioxo-2,3-dihydro-1H-indene-2-ylidene)propanedinitrile
(dicyanomethylene indane-1,3-dione, 3) was prepared according to
Chaterjee.35
Reaction of 4-substituted thiosemicarbazides 1a–f with 2-(1,3-
dioxo-2,3-dihydro-1H-inden-1-ylidene)propanedinitrile (3): A solu-
tion of thiosemicarbazides 1a–f (1.0 mmol) in 20 mL dry ethyl acetate
was added dropwise to a solution of 3 (208 mg, 1 mmol) in 30 mL of
dry ethyl acetate. The reaction mixture was magnetically stirred and
heated under reflux for 3h with (1a), 4h with (1b), 6h with (1c,d,e)
and 3h with (1f) (the reaction was followed by TLC analysis). Dark
reddish brown crystals were precipitate, filtered and washed with
ethanol to give compounds 7a–f. The filtrate was concentrated and
applied to 5 PLC-plates and developed with toluene/ethyl acetate
(5:1) to give numerous coloured zones. The most intense of which was
removed and extracted with acetone and recrystallised to give
compounds 8a–e.
5′-Amino-4′-cyano-N-phenyl-1,3-dioxo-1,3-dihydrospiro[indene-2,3′-
pyrazole]-2′(1′H)-carbothioamide (7a): Dark reddish brown crystals
(0.266 g, 71%), m.p. 280–282 °C (acetonitrile). 1H NMR (DMSO-d6):
δ = 6.97 (br, 2H, NH2), 7.00–7.95 (m, 9H, ArH), 9.85 (br, 1H, NH-Ph),
10.95 (br, 1H, pyrazole-NH). 13C NMR (DMSO-d6): δ = 59.73 (C-4′),
106.76 (spiro-C-2,3′), 119.45 (CN), 126.79, 127.95, 128.04, 130.83
(ArCH), 138.11, 138.38, 139.04 (ArC), 174.68 (C-5′), 186.01(C=S),
193.13 and 194.56 (CO). IR (KBr): υ (cm−1) = 3410-3150 (NH2, NH),
2210 (CN), 1750 and 1740 (CO), 1600 (ArC=C), 1570 (NH-def. and
C–N str.), 1365, 995 (C=S and C–N). MS, m/z (%) = 375 [M+]
(28), 348 (100), 282 (42), 254 (64), 135 (72), 91 (86), 77 (52).
C19H13N5O2S (375.40): Calcd: C, 60.79; H, 3.49; N, 18.66; S, 8.54.
Found: C, 60.93; H, 3.41; N, 18.52; S, 8.69%.
Experimental
The uncorrected melting points were determined on a Gallenkamp
melting point apparatus; IR spectra were recorded using KBr disks on
Shimadzu 408 instrument. 1H NMR 400 MHz and 100 MHz 13C NMR
spectra were recorded on a Bruker AM 400 spectrometer in CDCl3 or
DMSO-d6 in 5mm tubes at RT, with the deuterium signal of the sol-
vent as the lock and TMS as internal references, s = singlet, m = mul-
tiplet, br = broad. DEPT spectra 135/90 were run in a standard manner
to separate the CH/CH3 and CH2 lines phased “up” and “down”,
respectively. The mass spectra (70 eV, electron impact mode) were
recorded on a Finnigan MAT instrument. Combustion analyses were
run at the Microanalytical Centre, Cairo University, Egypt. Prepara-
tive layer chromatography (PLC) was carried out using air dried
1.0 mm thick layers of slurry of Silica gel (Merck Pf 254) applied on
48 cm wide and 20 cm high glass plates using toluene/ethyl acetate
as developing solvent. Zones were detected by their colour or by
quenching of 254 nm light and extracted out with acetone.
5′-Amino-4′-cyano-N-benzyl-1,3-dioxo-1,3-dihydrospiro[indene-2,3′-
pyrazole]-2′(1′H)-carbothioamide (7b): Dark reddish brown crystals
1
(0.268 g, 69%), m.p. 292–294 °C (methanol). H NMR (DMSO-d6):
δ = 4.80 (s, 2H, CH2-Ph), 6.94 (br, 2H, NH2), 7.10–7.95 (m, 9H, ArH),
8.80 (br, 1H, NH), 11.0 (br, 1H, pyrazole-NH). 13C NMR (DMSO-d6):
δ = 46.51 (CH2), 59.73 (C-4′), 106.76 (spiro-C-2,3′), 119.33 (CN),
126.79, 127.38, 127.91, 128.09, 131.69 (ArH), 137.57, 138.42, 139.39
(ArC), 173.66 (C-5′), 187.94 (C=S), 193.17, 194.36 (CO). IR (KBr):
υ (cm−1) = 3430-3220 (NH2, NH), 2215 (CN), 1745 and 1735 (CO),
1610 (ArC=C), 1570 (NH-def. and C–N str.), 1350, 1000 (C=S, C–N).
MS, m/z (%) = 389 [M+] (17), 362 (76), 274 (25), 104 (28), 91 (100),
65 (47). C20H15N5O2S (389.43): Calcd: C, 61.68; H, 3.88; N, 17.98;
S, 8.23. Found: C, 61.85; H, 3.76; N, 18.12; S, 8.36%.
N-Allyl-5′-amino-4′-cyano-1,3-dioxo-1,3-dihydrospiro[indene-2,3′-
pyrazole]-2′(1′H)-carbothioamide (7c): Dark reddish brown crystals
(0.230 g, 68%), m.p. 240–242 °C (dec.) (ethanol). 1H NMR (DMSO-
d6): δ = 4.35 (m, 2H, allyl-CH2–N), 5.25 (m, 2H, allyl-CH2=), 5.90
(m, 1H, allyl-CH=), 6.90 (br, 2H, NH2), 7.15–7.90 (m, 5H, ArH and
allyl-NH), 11.02 (br, 1H, pyrazole-NH). 13C NMR (DMSO-d6): δ =
56.62 (allyl-CH2N), 59.72 (C-4′), 106.72 (spiro-C-2,3′), 114.62 (allyl-
CH2=), 116.68 (CN), 127.09, 130.04 (ArCH), 134.86, 137.56 (ArC),
170.31 (C-5′), 181.34 (C=S), 193.18, 194.40 (CO). IR (KBr): υ (cm−1)
= 3430–3210 (NH2, NH), 2210 (CN), 1750 and 1735 (CO), 1620
(ArC=C), 1575 (NH-def. and C–N str.), 1360, 1010 (C=S, C–N).
MS, m/z (%): 339 [M+] (12), 312 (18), 273 (36), 245 (42), 99 (64),
Fig. 4

496 JOURNAL OF CHEMICAL RESEARCH 2010
Scheme 3
41 (100). C16H13N5O2S (339.37): Calcd: C, 56.63; H, 3.86; N, 20.64;
S, 9.45. Found: C, 56.76; H, 3.99; N, 20.46; S, 9.61%.
5′-Amino-4′-cyano-N-(4-fluorophenyl)-1,3-dioxo-1,3-dihydrospiro
1620 (ArC=C), 1570 (NH-def. and C–N str.), 1360, 980 (C=S and
C–N). MS, m/z (%): 443 [M+] (12), 377 (100), 204 (47), 160 (18), 104
(23). C20H12F3N5O2S (443.40): Calcd: C, 54.18; H, 2.73; N, 15.79; S,
7.25. Found: C, 53.97; H, 2.85; N, 15.92; S, 7.08%.
[indene-2,3′-pyrazole]-2′(1′H)-carbothioamide (7d): Dark brown
1
crystals (0.247 g, 63%), m.p. 296–298 °C (acetonitrile). H NMR
4-Phenyl-3-Thioxo-3H-indeno[1,2-e][1,2,4]-triazin-9(4H)-one ( 8a):
Yellowish brown crystals (0.070 g, 24%), m.p. 171–173 °C (ethanol).
1H NMR (DMSO-d6): δ = 7.05–7.50 (m, 7H, Ar), 7.65–7.90 (m, 2H,
Ar), 13C NMR (DMSO-d6): δ = 127.37, 128.20, 128.76, 129.77, 129.90
(ArCH), 130.34, 134.50, 135.08 (ArC), 139.10 (C-9a), 140.43 (C-4a),
185.85 (C=S), 193.01 (CO). IR (KBr): υ (cm−1) = 1715 (CO), 1610,
1585 (ArC=C), 1365,1005 (C=S and C–N). MS, m/z (%) = 291 [M+]
(16), 247 (66), 219 (61), 191 (53), 135 (22), 128 (41), 104 (46),
77 (100). C16H9N3OS (291.05): Calcd: C, 65.95; H, 3.11; N, 14.42;
S, 11.01. Found: C, 66.12; H, 3.03; N, 14.28; S, 10.94%.
(DMSO-d6): δ = 6.94 (br, 2H, NH2), 7.21–7.94 (m, 8H, ArH), 9.84
(br, 1H, NH-Ph), 10.98 (br, 1H, pyrazole-NH). 13C NMR (DMSO-d6):
δ = 60.26 (C-4′), 105.98 (spiro-C-2,3′), 119.11 (CN), 125.63, 128.55,
131.27, 132.15 (ArCH), 134.27, 137.92 (ArC), 162.86 (ArC-F),
173.65 (C-5′), 183.84 (C=S), 193.89, 195.12 (CO). IR (KBr): υ (cm−1)
= 3390-3205 (NH2, NH), 2220 (CN), 1750 and 1735 (CO), 1610
(ArC=C), 1575 (NH-def. and C–N str.), 1350, 1000 (C=S and C–N).
MS, m/z (%): 393 [M+] (42), 366 (29), 338 (36), 304 (44), 234 (28),
219 (82), 166 (44), 154 (100), 110 (35), 91 (52). C19H12FN5O2S
(393.39): Calcd: C, 58.01; H, 3.07; N, 17.80; S, 8.15. Found: C, 57.84;
H, 2.96; N, 17.92; S, 7.96%.
4-Benzyl-3-Thioxo-3H-indeno[1,2-e][1,2,4]-triazin-9(4H)-one ( 8b).
1
Brown crystals (0.070 g, 23%), m.p. 188–190 °C (acetonitrile). H
NMR (DMSO-d6): δ = 4.95 (s, 2H, CH2), 7.20–8.10 (m, 9H, ArH). 13
C
5′-Amino-4′-cyano-N-(3,5-difluorophenyl)-1,3-dioxo-1,3-dihydrospiro
[indene-2,3′-pyrazole]-2′(1′H)-carbothioamide (7e): Dark brown
crystals (0.263 g, 64%), m.p. 309–311 °C (acetonitrile). H NMR
NMR (DMSO-d6): δ = 47.87 (CH2), 127.68, 127.88, 128.18, 128.38,
128.63 (ArCH), 129.95, 135.98, 136.31 (ArC), 139.98 (C-9a), 142.09
(C-4a), 186.72 (C=S), 193.12 (CO). IR (KBr): υ (cm−1) = 1710 (CO),
1620, 1580 (ArC=C), 1370, 1010(C=S and C–N). MS, m/z (%) = 305
[M+] (9), 261 (21), 149 (24), 128 (36), 104 (56), 91 (100), 77 (58).
C17H11N3OS (305.35): Calcd: C, 66.87; H, 3.63; N, 13.76; S, 10.50.
Found: C, 67.02; H, 3.51; N, 13.88; S, 10.37%.
4-Allyl-3-Thioxo-3H-indeno[1,2-e][1,2,4]-triazin-9(4H)-one (8c).
Brown crystals (0.066 g, 26%), m.p. 120–122 °C (ethanol). 1H NMR
(DMSO-d6): δ = 4.30 (m, 2H, allyl-CH2N), 5.22 (m, 2H, allyl-CH2 ),
5.95 (m, 1H, allyl-CH=), 7.55–8.20 (m, 4H, ArH). 13C NMR (DMSO-
d6): δ = 47.36 (allyl-CH2-N), 118.31 (allyl CH2=), 129.07, 131.97,
133.65 (ArCH), 134.28 (allyl-CH=), 136.32, 136.44 (ArC), 139.85
(C-9a), 141.70 (C-4a), 185.57 (C=S), 193.46 (CO). IR (KBr): υ (cm−1)
= 1720 (CO), 1595 (ArC=C), 1365, 995 (C=S and C–N). MS, m/z (%)
= 255 [M+] (14), 156 (26), 128 (52), 104 (33), 77 (47), 41 (100).
C13H9N3OS (255.30): Calcd: C, 61.16; H, 3.55; N, 16.46; S, 12.56.
Found: C, 60.97; H, 3.66; N, 16.63; S, 12.33%.
1
(DMSO-d6): δ = 6.82 (br, 2H, NH2), 7.02–7.86 (m, 7H, ArH), 9.62
(br, 1H, NH-Ph), 10.80 (br, 1H, pyrazole-NH). 13C NMR (DMSO-d6):
δ = 60.74 (C-4′), 107.22 (spiro-C-2,3′), 118.87 (CN), 123.93, 126.77,
130.88, 132.22 (ArCH), 135.24, 138.17 (ArC), 160.12 (ArC-F),
173.54 (C-5′), 182.66 (C=S), 193.46, 194.85 (CO). IR (KBr):
υ (cm−1) = 3410-3190 (NH2, NH), 2215 (CN), 1745 and 1725 (CO),
1615 (ArC=C), 1575 (NH-def. and C–N str.), 1355, 995 (C=S and
C–N). MS, m/z (%): 411 [M+] (6), 384 (17), 367 (19), 304 (100), 171
(22), 113 (26), 104 (35). C19H11F2N5O2S (411.38): Calcd: C, 55.47;
H, 2.70; N, 17.02; S, 7.79. Found: C, 55.63; H, 2.59; N, 16.84;
S, 7.71%.
5′-Amino-4′-cyano-1,3-dioxo-N-[4-(trifluoromethyl)phenyl)-1,3-
dihydrospiro[indene-2,3′-pyrazole]-2′(1′H)-carbothioamide
(7f):
Reddish brown crystals (0.297 g, 67%), m.p. 326–328 °C (methanol).
1H NMR (CDCl3): δ = 7.02 (br, 2H, NH2), 7.21–8.01 (m, 8H, ArH),
9.97 (br, 1H, NH-Ph), 11.07 (br, 1H, pyrazole-NH). 13C NMR (CDCl3):
δ = 60.59 (C-4′), 106.27 (spiro-C-2,3′), 118.88 (CN), 125.17 (C-F3),
126.83, 129.74, 130.82, 131.75 (ArCH), 133.22, 135.12, 137.66
(ArC), 172.82 (C-5′), 184.17 (C=S), 193.76, 194.95 (CO). IR (KBr):
υ (cm−1) = 3380–3220 (NH2, NH), 2210 (CN), 1755 and 1740 (CO),
4-(3,5-Difluorophenyl)-3-Thioxo-3H-indeno[1,2-e][1,2,4]-triazin-
9(4H)-one (8d). Orange crystals (0.056 g, 17%), m.p. 210–212 °C
1
(dec.) (ethanol). H NMR (DMSO-d6): δ = 7.24–7.86 (m, 7H, ArH).
13C NMR (DMSO-d6): δ = 123.16, 124.27, 128.72, 129.83, 129.96

JOURNAL OF CHEMICAL RESEARCH 2010 497
8
9
F.A. El-Essawy, A.F. Khattab and A.A.-H. Abdel-Rahman, Monatsh.
Chem., 2007, 138, 77.
O.F. Öztür, Trans. Met. Chem., 2007, 32,224.
(ArCH), 134.87, 135.92, 136.12 (ArC), 139.37 (C-9a), 140.58 (C-4a),
160.27 (ArC-F), 185.76 (C=S), 193.16 (CO). IR (KBr): υ (cm−1) =
1710 (CO), 1620, 1580 (ArC=C), 1360, 995 (C=S and C–N). MS, m/z
(%) = 327 [M+] (18), 299 (12), 283 (11), 171 (76), 128 (46), 104 (87),
76 (100). C16H7F2N3OS (327.31): Calcd: C, 58.71; H, 2.16; N, 12.84;
S, 9.80. Found: C, 58.56; H, 2.27; N, 13.03; S, 9.67%.
3-Thioxo-4-[4-(trifluoromethyl)phenyl]-3H-indeno[1,2-e][1,2,4]-
triazin-9(4H)-one (8e): Reddish orange crystals (0.072 g, 20%), m.p.
270–272 °C (dec.) (acetonitrile). 1H NMR (DMSO-d6): δ = 7.18–8.02
(m, 8H, ArH). 13C NMR (DMSO-d6): δ = 127.27, 127.78, 128.28,
129.51, 129.86 (ArCH), 131.12, 135.84, 136.77, 137.46 (ArC), 140.26
(C-9a), 141.83 (C-4a), 185.81 (C=S), 193.42 (CO). IR (KBr): υ (cm−1)
= 1710 (CO), 1615, 1590 (ArC=C), 1355, 1010 (C=S and C–N). MS,
m/z (%) = 359 [M+] (12), 331 (16), 303 (10), 200 (51), 159 (27), 128
(27), 104 (81), 76 (100). C17H8F3N3OS (359.33): Calcd: C, 56.82; H,
2.24; N, 11.69; S, 8.92. Found: C, 56.97; H, 2.18; N, 11.87; S,
9.07%.
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Received 8 June 2010; accepted 7 July 2010
Paper 1000184 doi: 10.3184/030823410X12810986062376
Published online: 7 October 2010
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