Formation of dioxospiroindene[1, 3]thiazine and thioxoindeno[2, 1-]imidazolone derivatives from alkenylidene-hydrazinecarbothioamides

Article abstract of DOI:10.2478/s11696-012-0145-3

The reaction of (substituted) alkenylidene-hydrazinecarbothioamides with 2-(1, 3-dioxo-2, 3- dihydro-1H-inden-2-ylidene)propanedinitrile led to the formation of 1, 3-dioxospiroindene[1, 3]- thiazine and thioxoindeno[2, 1-d]imidazolone derivatives in modes

Full text of DOI:10.2478/s11696-012-0145-3

Chemical Papers 66 (4) 295–303 (2012)
DOI: 10.2478/s11696-012-0145-3
ORIGINAL PAPER
Formation of dioxospiroindene[1,3]thiazine and
thioxoindeno[2,1- ]imidazolone derivatives from
alkenylidene-hydrazinecarbothioamides
a
a
aAlaa A. Hassan*, Ahmed M. Nour El-Din, Fathy F. Abdel-Latif,
aSara M. Mostafa, Stefan Bräse
b
aChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt
bInstitute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Received 7 September 2011; Revised 8 January 2012; Accepted 8 January 2012
The reaction of (substituted) alkenylidene-hydrazinecarbothioamides with 2-(1,3-dioxo-2,3-
dihydro-1H-inden-2-ylidene)propanedinitrile led to the formation of 1,3-dioxospiroindene[1,3]-
thiazine and thioxoindeno[2,1-d]imidazolone derivatives in modest yields. In addition, 1,3-
dihydroxyindan-2-ylidenepropanedinitrile was found. Explanations of these conversions involving
nucleophilic reactions and condensations are presented.
c
ꢀ 2012 Institute of Chemistry, Slovak Academy of Sciences
Keywords: alkenylidene-hydrazinecarbothioamides, dioxospiroindene[1,3]thiazine, thioxoindeno
[2,1-d]imidazolone
Introduction
bohydrazides (Hassan et al., 1997), and substituted
carbohydrazides (Hassan et al., 2009) were reported.
The aroyl thiourea derivatives and II in acetic acid
(100 %) afforded indenothiazepine derivatives rather
than spiroindolothiazines (Aly et al., 2010). Heterocy-
clisation of thiosemicarbazones is induced by various
metallic salts (Noto et al., 1996, 1995, 1999; Grut-
tadauia et al., 1993; Ernst et al., 1995; Invidiata et
al., 1997) or by dienophilic reagents (Gomaa et al.,
2006; Darehkordi et al., 2007).
On other occasions, the cyclisation mechanism in-
volves a plain oxidation step (electron abstraction
or dehydrogenation) prior to the actual ring closure
step (Tsoungas & Diplas, 2003). These intriguing
transformations prompted us to investigate the re-
actions of alkenylidene-hydrazinecarbothioamides Ia–
Ie (bearing substituents), a selection of aryl, alkenyl,
and alkyl substituents with II to synthesise important
spiro- and fused heterocyclic systems.
2-(1,3-Dioxo-2,3-dihydro-1H-inden-2-ylidene)pro-
panedinitrile ((2-dicyanomethylidene)indan-1,3-dione,
II ) is the weakest acceptor (Bespalov et al., 1980) in
the series of related organic π-acceptors such as tetra-
cyanoethene and (2,5-cyclohexadiene-1,4-diylidene)-
dimalononitrile,
7,7,8,8-tetracyanoquinodimethane
(tetracyanoquinodimethane) which also readily form
addition products with organic nucleophiles (Junek et
al., 1972; Rappoport & Ladkani, 1973; Boila-Go¨ckel
et al., 1996; Hanefeld et al., 1996; Junek et al., 1990;
D¨opp et al., 2002, 2006, 1996; Hassan & Shehatta,
2007; Hassan et al., 2009). N,Nꢀ-diarylacetamidines
reacted with II to form indenoazepine-6-ones during
nucleophilic attack by N-2 of acetamidines on a cyano
group of II (Do¨pp et al., 1996). The reaction of II with
1-substituted-2,5-dithiobiureas (Hassan et al., 2007),
acylthiosemicarbazides (Hassan et al., 2008a), thiocar-
*Corresponding author, e-mail: alaahassan2001@yahoo.com

296
A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
Fig. 1. The products from the reaction between Ia–Ie and II.
Experimental
mmol) in the same solvent with two drops of acetic an-
hydride upon stirring at room temperature. The solu-
tion mixture was stirred for 3 h, left to stand overnight
and poured into 250 mL of ice/water. The precipi-
tate was removed by filtration and allowed to crys-
tallise from ethanol to give colourless crystals of Ia–Ie.
(2-Dicyanomethylidene)indan-1,3-dione (II ) was pre-
pared following the method described by Chaterjee
(1969).
Melting points were determined using open glass
capillaries on a Gallenkamp melting point apparatus
(Gallenkanp, UK) and the values remain uncorrected.
Elemental analyses were determined by the Microan-
alytical Center, Cairo University, Egypt using Elmyer
306, (Germany). The IR spectra were recorded on a
Shimadzue 408 instrument (Japan), using potassium
1
bromide discs. The H NMR (400.13 MHz) and 13C
NMR (100.6 MHz) spectra were observed on a Bruker
AM400 spectrometer (Germany) with tetramethylsi-
lane as the internal standard; chemical shifts are ex-
pressed as δ. The 13C NMR signals were assigned on
the basis of DEPT 135/90 spectra. The mass spec-
tra were obtained on a Finnigan MAT 312 (Germany)
instrument using electron impact ionisation (70 eV).
Air-dried 1.0 mm thick layers of the silica gel slurry
applied (Merck PF254, Germany) onto 48 cm wide
and 20 cm high glass plates using the solvents listed
were used in preparative layer chromatography (plc).
Zones were eluted with acetone and detected by fluo-
rescence indicator quenching upon 254 nm light.
Reaction of alkenylidene-hydrazinecarbothio-
amides (Ia–Ie) with (2-dicyanomethylidene)
indan-1,3-dione (II)
To a solution of II (208 mg, 1 mmol) in dry
ethyl acetate (20 mL), a solution of Ia–Ie (1 mmol)
in dry ethyl acetate, (10 mL) was added with stir-
ring. The mixture was refluxed for 4–6 h until the
starting materials were consumed (as monitored by
TLC). The precipitate was filtered, washed with cold
ethyl acetate and identified as 1,3-dihydroxyindan-
2-ylidenepropanedinitrile IV. The filtrate was pre-
concentrated, applied to 5 plc plates and developed
using toluene/ethyl acetate (ϕr = 1 : 1 for the reac-
tions with Ia, Ib, Ie and ϕr = 2 : 1 for Ic, Id) to give a
number of coloured zones. Two intense zones were ex-
tracted with acetone. The fastest migrating (reddish
brown) zone contained compounds Va–Vd; the slow-
est orange zone contained IIIa–IIIe. The products so
obtained were re-crystallised.
Preparation of substituted alkenylidene-
hydrazinecarbothioamides (Ia–Ie)
A solution of the respective aldehyde (1.0 mmol)
in 5 mL dimethylsulphoxide was added drop-wise
into a solution of 4-substituted thiosemicarbazide (1.0

A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
297
Fig. 2. Four labile (1 : 1) adducts (VI–XI) from the reaction between I and II.
Results and discussion
in δ values for C-atoms observed in push-pull alkenes
(Kalinowski et at., 1984; Gewald & Schindler, 1990).
In addition, in the 13C NMR of IIIa–IIIe, spiro C-
2,6ꢀ is regularly shifted up-field at δ 57.7–56.6 and so
is in a range close to that found in the related sys-
tems (Va, Vc, and Vd, Hafez et al. (1986) and com-
pounds Xa–Xc, Gomaa and Do¨pp (1998)) compared
with spiro C-2,4ꢀ in the alternative structures X and
XII.
Solutions of Ia–Ie (1 mmol) in dry ethyl acetate
(10 mL) were added into a solution of II (1 mmol) in
dry ethyl acetate (20 mL); the mixtures were refluxed
for 4–6 h with the admission of air; the chromato-
graphic separation of the residue afforded a number of
coloured zones from which products III and V could
be isolated (Fig. 1).
4ꢀ-Amino-1,3-dioxo-3ꢀ-(substituted)-2ꢀ-(phenyl-
imino)-1,2ꢀ,3,3ꢀ-tetrahydrospiro( indene-2,6ꢀ-[1,3]thia-
zine)-5ꢀ-carbonitriles (IIIa–IIIe) were assigned on the
basis of the elemental analysis and spectral data.
The IR spectra of IIIa–IIIe showed strong absorp-
tion signals between 1730 cm−1 and 1720 cm−1 for
the carbonyl group, and between 3370–3290 cm−1 f−o1r
The mass spectrometry fragmentation of isolated
compounds was studied under electron ionisation.
The following common features of the fragmenta-
tion patterns are strong evidence for the assigned
— —
structures: loss of PhN
— —
C
S giving rise to the ion
m/z = 135 common in the spectra of all five com-
pounds. The resulting fragment ions undergo loss of
NH2, 2220–2210 cm−1 (C—N), and 1655–1645 cm
—
C
—
S, m/z = 104 (C H CO), and m/z
—
— —
RCH N—N
— —
—
6 4
—
1
(C=N). H NMR spectra showed broad exchangeable
= 66 (H N—C C—CN). The analytical data of com-
—
2
signals with (D2O) between δ 6.72–6.50 due to the
amino group, in addition to the aromatic protons.
The 1H NMR of IIIa showed the presence of multi-
pound III would also match other isomers of products
X–XV (Figs. 3–5).
Compounds Ia–Ie may react at least with their sul-
phur atom, N-2 and N-4 as nucleophilic sites. On the
other hand, it was reported that the methine carbon
of I acted as a nucleophile in the sense of a polarity
inversion (Diez et al., 1997; Aziz et al., 2007; El-Ka¨ım
et al., 2003; Hassan et al., 2008b). Thus, several op-
tions for the interaction between Ia–Ie and II may be
envisaged.
plet δ at 6.60–6.85 due to CH CH. In its 13C NMR
—
—
—
—
spectrum, the (Ar—CH CH—) group resonated at δ
124.9 and at δ 136.1. Also, 13C NMR of IIIa showed
signals at δ 57.6 (spiro–C-2,6ꢀ), δ 158.0 (C-2ꢀ), and δ
192.2 (C-1,3). The 13C NMR data of IIIa are in line
1
with the H NMR data insofar as the distinctive ap-
—
pearance of carbon signals representing CH N at δ
—
143.7. Thiazine-C-5ꢀ and C-4ꢀ resonated at δ 53.7 and
δ 168.4, respectively, in accordance with the trends
It is probable that all the products observed are
formed from one of the four labile (1 : 1) adducts (VI–

298
A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
Fig. 3. The isomeric products from the intermediateVI.
Fig. 4. The isomeric products from the intermediate VII.
IX) of II to I (Fig. 2). The isomeric products would be
III, X, and XI, if the reaction took place through (N-2
and SH), (N-2 and N-4), and (N-4 and azomethine–
CH), respectively, via the intermediate VI (Fig. 3).
Products XII and XIII could be isolated if the re-
action involved the participation of SH and N-4 or SH
and azomethine–CH, respectively via the adduct VII
(Fig. 4).
and XV could be isolated (Fig. 5).
Structures X, XI, XIII, XIV, and XV could be ex-
1
cluded on the basis of H NMR as well as 13C NMR
spectra. For the alternative structures XII, the spiro–
C-2,4ꢀ 13C-resonances are considerably down-field to
those which were observed (Gomaa & Do¨pp, 1998;
Hassan et al., 2006). Structures XII and XIV could
be excluded on the basis of fragmentation ions in the
mass spectra of isolated products and formation of
—
If N-4 attacked the C—N of II, adduct VIII was
—
— —
PhN
— —
—
— —
S as well as R—CH N—N
— —
observed followed by inter-molecular nucleophilic at-
C
C
S as frag-
—
tack either by SH or azomethine–CH, products XIV
ments, for example IIIa at m/z = 489, 447, 354, 210,

A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
299
Fig. 5. The isomeric products from the intermediate VIII.
Fig. 6. The mechanism of formation products III and V.

300
A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
Table 1. Spectral data of newly prepared compounds Ia–Ie, IIIa–IIIe, and Va–Vd
Compound
Spectral data
ꢀ
IR, ν˜/cm−1: 983, 1362 (C S, C—N), 1594, 1619 (Ar-C C), 2983 (Ali-CH), 3123 (Ar-CH), 3236, 3315 (NH s)
—
—
—
—
Ib
1
—
H NMR (CDCl3), δ: 3.90 (s, 3H, OCH3), 6.90–7.10 (m, 3H, Ar-H and CH CH), 7.14–7.17 (m, 2H, Ar-H), 7.32–7.35
—
—
—
(m, 3H, Ar-H), 7.58–7.60 (m, 3H, Ar-H), 8.00 (d, 1H, J = 9.4 Hz, CH N), 9.95 (br, 1H, NH)
13C NMR (CDCl3), δ: 55.5 (OCH3), 110.6, 120.7, 124.1, 124.8, 124.9, 125.8, 127.8, 128.0, 130.4 (Ar-CH), 134.4,
—
—
138.1 (Ar-C), 145.8 (CH N), 156.4 (Ar-C—O), 175.2 (C S)
—
—
MS, m/z (Ir/%): 311 (100) (M+), 280 (11), 135 (36), 91 (28), 77 (21)
ꢀ
IR, ν˜/cm−1: 983, 1324 (C S, C—N), 1595, 1644 (Ar-C C), 2988 (Ali-CH), 3142, 3292 (NH s)
—
—
—
—
Ic
1H NMR (CDCl3), δ: 0.85 (t, 3H, J = 6.7 Hz, CH3), 1.45 (m, 2H, CH2), 2.20–2.24 (m, 2H, CH2), 6.22 (d, 2H, J =
—
15.9 Hz, CH CH), 7.15–7.17 (m, 1H, Ar-H), 7.30–7.33 (m, 2H, Ar-H), 7.60–7.63 (m, 2H, Ar-H), 7.85 (d, 1H, J =
—
—
9.4 Hz, CH N), 9.85 (br, 1H, NH)
—
13C NMR (CDCl3), δ: 13.5 (CH3), 21.3 (CH2), 34.4 (CH2), 124.8, 124.9, 127.2, 127.9 (Ar-CH), 138.9 (Ar-C), 143.6
—
—
(Ar-CH), 145.2 (CH N), 175.4 (C S)
—
—
MS, m/z (Ir/%): 247 (100) (M+), 151 (76), 135 (64), 110 (51), 91 (48), 77 (41)
1
—
H NMR (CDCl3), δ: 1.85 (d, 3H, J = 6.6 Hz, CH3), 6.23–6.25 (m, 2H, CH CH), 7.15–7.17 (m, 1H, Ar-H), 7.35–7.38
—
Id
Ie
—
(m, 2H, Ar-H), 7.55 (m, 2H, Ar-H), 7.82 (d, 1H, J = 9.3 Hz, CH N), 9.80 (br, 1H, NH)
—
13
—
—
C NMR (CDCl3), δ: 18.5 (CH3), 125.9, 127.7, 128.0, 128.4 (Ar-CH), 138.9 (Ar-C), 141.2 (Ar-CH), 145.2 (CH N),
—
175.3 (C S)
—
MS, m/z (Ir/%): 219 (12) (M+), 192 (14), 151 (18), 135 (12), 77 (15), 41 (100)
IR, ν˜/cm−1: 981, 1379 (C S, C—N), 1599 (Ar-C C), 2998 (Ali-CH), 3064 (Ar-CH), 3151, 3301 (NH s)
ꢀ
—
—
—
—
1H NMR (CDCl3), δ: 1.12 (d, 6H, J = 6.5 Hz, 2 × CH3), 2.55–2.57 (m, 1H, CH), 7.15–7.18 (m, 1H, Ar-H), 7.33–7.35
—
(m, 2H, Ar-H), 7.50–7.52 (m, 1H, Ar-H), 7.60–7.63 (m, 2H, Ar-H and CH N), 9.70 (br, 1H, NH)
—
13
—
—
C NMR (CDCl3), δ: 19.5, 19.9 (CH3), 30.7 (CH), 125.3, 128.5, 129.4 (Ar-CH), 138.9 (Ar-C), 152.4, (CH N),
—
176.6 (C S)
—
MS, m/z (Ir/%): 221 (14) (M+), 178 (28), 151 (11), 135 (12), 91 (21), 77 (26), 43 (100)
—
—
IIIa
IIIb
IR, ν˜/cm−1: 1590, 1610 (Ar-C C), 1650 (C N), 1725 (CO), 2210 (C—N), 3290–3360 (NH2)
—
—
—
—
1
—
H NMR (CDCl3), δ: 6.51 (br, 2H, NH2), 6.60–6.85 (m, 2H, CH CH), 7.14–7.35 (m, 8H, Ar-H), 7.80–7.84 (m, 7H,
—
—
Ar-H and CH N)
—
13
ꢀ
ꢀ
—
C NMR (CDCl3), δ: 53.7 (C-5 ), 57.6 (spiro-C-2,6 ), 118.8 (C—N), 124.9, 126.2, 127.2, 127.5, 128.8, 129.0, 129.1,
129.3, 129.8, 135.6, 136.1 (Ar-CH), 140.6, 142.0 (Ar-C), 143.7 (CH N), 158.0 (C-2 ), 168.4 (C-4 ), 192.2 (C O)
MS, m/z (Ir/%): 489 (8) (M+), 447 (12), 354 (10), 210 (22), 206 (48), 188 (7), 135 (76), 129 (100), 104 (33), 91
—
ꢀ
ꢀ
—
—
—
—
(42), 77 (51), 66 (15)
IR, ν˜/cm−1: 1610 (Ar-C C), 1655 (C N), 1730 (C O), 2215 (C—N), 3300–3350 (NH2)
H NMR (CDCl3), δ: 3.85 (s, 3H, OCH3), 6.55 (br, 2H, NH2), 6.88–6.95 (m, 2H, CH CH), 7.10–7.15 (m, 2H,
Ar-H), 7.22–7.38 (m, 5H, Ar-H), 7.40–7.53 (m, 4H, Ar-H), 7.90 (m, 2H, Ar-H), 8.00 (d, 1H, J = 9.4 Hz, CH N)
C NMR (CDCl3), δ: 54.3 (C-5 ), 54.4 (OCH3), 57.7 (spiro-C-2,6 ), 110.0 (Ar-CH), 119.5 (C—N), 123.9, 125.8,
—
—
—
—
—
—
—
—
1
—
—
—
—
13
ꢀ
ꢀ
—
—
—
—
125.9, 126.8, 126.9, 127.2, 128.6, 128.7, 129.3, 130.8 (Ar-CH), 134.5, 134.7, 135.7 (Ar-C), 142.9 (CH N), 158.6
ꢀ
ꢀ
—
(C-2 ), 159.1 (Ar-C—OCH3), 167.9 (C-4 ), 192.5 (C O)
—
MS, m/z (Ir/%): 519 (11) (M+), 504 (9), 332 (26), 318 (14), 261 (29), 218 (7), 145 (22), 135 (64), 104 (45), 77 (100),
66 (46)
IR, ν˜/cm−1: 1600 (Ar-C C), 1645 (C N), 1725 (C O), 2220 (C—N), 3310–3340 (NH2)
—
— —
— —
—
—
—
IIIc
1H NMR (CDCl3), δ: 0.90 (t, 3H, J = 6.7 Hz, CH3), 1.40 (m, 2H, CH2), 2.18 (m, 2H, CH2), 6.23 (m, 2H, CH=CH),
6.72 (NH2), 7.22–7.30 (m, 2H, Ar-H), 7.32–7.46 (m, 2H, Ar-H), 7.48–7.56 (m, 2H, Ar-H), 7.59–7.75 (m, 2H, Ar-H),
—
7.93 (d, 1H, J = 9.3 Hz, CH N)
—
13
ꢀ
ꢀ
—
—
—
C NMR (CDCl3), δ: 12.7 (CH3), 20.7 (CH2), 33.9 (CH2), 52.6 (C-5 ), 56.6 (spiro-C-2,6 ), 119.5 (C—N), 124.1,
126.7, 128.5, 128.8, 130.8, 131.3 (Ar-CH), 133.5, 134.6 (Ar-C), 144.1 (Ar-CH), 146.4 (CH N), 158.2 (C-2 ), 167.4
—
ꢀ
ꢀ
—
(C-4 ), 191.7 (C O)
—
MS, m/z (Ir/%): 455 (21) (M+), 413 (41), 370 (46), 245 (53), 210 (41), 154 (12), 135 (100), 91 (78), 77 (74), 66 (39)
—
—
IIId
IIIe
IR, ν˜/cm−1: 1610 (Ar-C C), 1645 (C N), 1720 (C O), 2210 (C—N), 3310–3350 (NH2)
—
— —
— —
—
1
—
H NMR (CDCl3), δ: 1.80 (d, 3H, J = 6.5 Hz, CH3), 6.26 (m, 2H, CH CH), 6.50 (br, 2H, NH2), 7.20–7.55 (m,
5H, Ar-H), 7.60–7.76 (m, 4H, Ar-H), 7.84 (d, 1H, J = 9.3 Hz, CH N)
C NMR (CDCl3), δ: 17.6 (CH3), 53.1 (C-5 ), 57.1 (spiro-C-2,6 ), 119.2 (C—N), 124.7, 127.5, 128.1, 128.6, 128.7,
130.8 (Ar-CH), 134.5, 135.5 (Ar-C), 138.8 (Ar-CH), 143.8 (CH N), 157.3 (C-2 ), 168.2 (C-4 ), 191.6 (C O)
MS, m/z (Ir/%): 427 (9) (M+), 371 (18), 329 (34), 292 (21), 217 (72), 210 (91), 135 (100), 126 (8), 104 (72), 77
—
—
—
13
ꢀ
ꢀ
—
—
—
—
ꢀ
ꢀ
—
—
(68), 66 (31)
IR, ν˜/cm−1: 1595, 1610 (Ar-C C), 1655 (C N), 1730 (C O), 2215 (C—N), 3290–3370 (NH2)
1H NMR (CDCl3), δ: 1.14 (d, 6H, J = 6.5 Hz, 2 × CH3), 2.48 (m, 1H, CH), 6.61 (br, 2H, NH2), 7.20–7.76 (m, 9H,
—
—
—
—
—
—
—
—
—
Ar-H), 7.83 (d, 1H, J = 9.3 Hz, CH N)
—
13
ꢀ
ꢀ
—
C NMR (CDCl3), δ: 19.9 (CH3), 29.5 (CH), 52.9 (C-5 ), 56.8 (spiro-C-2,6 ), 119.2 (C—N), 126.7, 127.3, 128.0,
—
ꢀ
ꢀ
—
—
—
128.3, 130.1 (Ar-CH), 134.7, 135.9 (Ar-C), 152.76 (CH N), 157.3 (C-2 ), 167.9 (C-4 ), 192.6 (C O)
—
MS, m/z (Ir/%): 429 (8) (M+), 363 (14), 333 (12), 292 (21), 279 (19), 220 (65), 179 (51), 150 (46), 135 (31), 128
(6), 104 (100), 77 (46), 66 (21)

A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
301
Table 1. (continued)
Compound
Spectral data
—
—
Va
IR, ν˜/cm−1: 995, 1360 (C S, C—N), 1590, 1610 (Ar-C C), 1685 (C O)
— —
— —
1
—
H NMR (CDCl3), δ: 6.80 (m, 2H, CH CH), 6.90–7.10 (m, 3H, Ar-H), 7.16–7.76 (m, 11H, Ar-H), 7.98 (d, 1H, J
—
—
= 9.4 Hz, CH N)
—
13C NMR (CDCl3), δ: 117.8 (C-8a), 119.8, 125.0, 126.2, 126.6, 127.0, 127.4, 127.6, 127.9, 128.3, 128.8, 129.2, 130.5
—
—
—
(Ar-CH), 132.0 (C-3a), 132.2, 134.4, 135.0, 136.5 (Ar-C), 140.7 (CH N), 181.2 (C S), 188.9 (C O)
—
—
—
MS, m/z (Ir/%): 407 (100) (M+), 303 (22), 272 (9), 263 (47), 135 (52), 104 (34), 91 (67), 77 (45)
—
—
—
—
Vb
IR, ν˜/cm−1: 1010, 1355 (C S, C—N), 1585, 1615 (Ar-C C), 1690 (C O)
—
—
1
—
H NMR (CDCl3), δ: 3.85 (s, 3H, OCH3), 6.80–6.90 (m, 3H, CH CH and Ar-H), 7.00–7.40 (m, 6H, Ar-H), 7.50–7.65
(m, 6H, Ar-H), 8.00 (d, 1H, J = 9.3 Hz, CH N)
13C NMR (CDCl3), δ: 55.5 (OCH3), 110.6 (C-8a), 111.0, 122.9, 125.0, 125.3, 126.0, 126.5, 127.4, 128.1, 128.9, 129.8,
—
—
—
—
130.0, 130.2, 131.5 (Ar-CH), 132.5 (C-3a), 133.2, 135.4, 135.7, 137.6 (Ar-C), 146.2 (CH N), 157.6 (Ar-C—O), 182.3
—
—
—
(C S), 189.1 (C O)
—
—
MS, m/z (Ir/%): 437 (11) (M+), 391 (51), 302 (6), 271 (100), 210 (391), 135 (26), 104 (52), 91 (44), 77 (67)
IR, ν˜/cm−1: 1000, 1345 (C S, C—N), 1600, 1605 (Ar-C C), 1690 (C O)
— —
— —
—
—
Vc
1H NMR (CDCl3), δ: = 0.90 (t, 3H, J = 6.7 Hz, CH3), 1.40 (m, 2H, CH2), 2.15 (m, 2H, CH2), 6.10 (dd, 2H, J =
—
15.8 Hz, CH CH), 6.95 (m, 2H, Ar-H), 7.15–7.40 (m, 5H, Ar-H), 7.50–7.63 (m, 2H, Ar-H), 7.80 (d, 1H, J = 9.4 Hz,
—
—
CH N)
—
13C NMR (CDCl3), δ: 12.6 (CH3), 20.8 (CH2), 33.9 (CH2), 119.7 (C-8a), 124.9, 125.3, 127.1, 127.2, 128.6, 128.9,
—
—
130.5, 131.5 (Ar-CH), 132.2 (C-3a), 132.7, 134.4, 136.6 (Ar-C), 144.1 (Ar-CH), 148.6 (CH N), 181.2 (C S), 188.9
—
—
—
(C O)
—
MS, m/z (Ir/%): 373 (37) (M+), 330 (100), 277 (18), 264 (22), 238 (6), 135 (26), 91 (32), 77 (27)
—
—
Vd
IR, ν˜/cm−1: 985, 1360 (C S, C—N), 1580, 1600 (Ar-C C), 1695 (C O)
— —
— —
1H NMR (CDCl3), δ: 1.30 (d, 6H, J = 6.4 Hz, 2 × CH3), 2.50 (m, 1H, CH), 7.00 (m, 5H, Ar-H), 7.30–7.65 (m, 5H,
—
Ar-H and CH N)
—
13C NMR (CDCl3), δ: 22.0 (CH3), 29.9 (CH), 122.4 (C-8a), 126.2, 127.1, 127.9, 128.5, 128.8, 129.0, 129.5 (Ar-CH),
—
—
—
131.5 (C-3a), 135.3, 136.5, 138.1 (A-C), 153.3 (CH N), 181.1 (C S), 189.2 (C O)
—
—
—
MS, m/z (Ir/%): 347 (9) (M+), 304 (11), 219 (100), 204 (32), 149 (63), 135 (29), 91 (24), 77 (34)
Table 2. Characterisation data of newly prepared compounds Ib–Ie, IIIa–IIId, and Va–Vd
wi(calc.)/%
wi(found)/%
Yield
M.p.
Compounda
Formula
Mr
C
H
N
S
%
◦C
Ib
Ic
C17H17N3OS
C13H17N3S
311.40
247.36
221.10
489.55
519.57
455.53
427.48
429.49
407.49
437.51
373.47
347.43
65.57
65.65
63.12
62.97
59.69
59.82
68.70
68.86
67.04
66.87
65.92
66.14
64.62
64.78
64.32
64.51
73.69
73.87
71.38
71.16
70.75
70.94
69.14
68.91
5.50
5.41
6.93
7.07
6.83
6.74
3.91
4.07
4.07
3.93
4.65
4.49
4.01
3.93
4.46
4.43
4.21
4.32
4.38
4.47
5.13
4.98
4.93
5.02
13.49
13.60
16.99
17.14
18.99
19.22
14.31
14.19
13.48
13.65
15.37
15.51
16.38
16.22
16.31
16.52
10.31
10.13
9.60
10.30
10.17
12.96
12.79
14.49
14.34
6.55
6.73
6.17
6.04
7.04
6.88
7.50
7.66
7.47
7.32
7.87
7.98
7.33
7.15
8.59
8.73
9.23
9.39
89
190
81
77
53
46
49
47
41
28
29
31
28
152
144
300
315
290
274
280
238
260
220
205
Ie
C11H15N3S
IIIa
IIIb
IIIc
IIId
IIIe
Va
C28H19N5O2S
C29H21N5O3S
C25H21N5O2S
C23H17N5O2S
C23H19N5O2S
C25H17N3OS
C26H19N3O2S
C22H19N3OS
C20H17N3OS
Vb
Vc
Vd
9.76
11.25
11.42
12.09
11.93
a) Physical-chemical data of compounds Ia and Id are in accordance with literature (Shah & Trivedi, 1963; Grammaticakis, 1950,
1953).

302
A. A. Hassan et al./Chemical Papers 66 (4) 295–303 (2012)
206, 188, 135, 129, 104, 91, 77, and 66. Only the struc-
ture of IIIa–IIIe, however, accommodates all the spec-
tral data listed above.
dione, (II ) providing several electrophilic sites. Thus,
—
thiaheterocycles S—C—N + C—N or N—(CS)—N +
—
C2 mode of cyclisation are favoured. Both spiroanel-
lated 1,3-thiazines and fused imidazolines are formed.
The results of combustion analysis and spectro-
scopic data suggested the presence of thioxoindenoim-
idazolone derivatives Va–Vd as one of the products
from the reaction between Ia–Ie and II. The molecu-
lar formula C22H19N3OS for Vc was confirmed by the
mass spectrum which exhibited the molecular ion at
m/z = 373 (37 %) and the fragmentation pattern at
m/z = 373, 330, 277, 264, 238, 135, 91, 77. The IR
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1
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—
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—
—
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—
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1
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