[4+2]cycloaddition reactions involving 2-arylmethylidene-1-thiooxoindan intermediates and antimicrobial activity evaluation of some products

Article abstract of DOI:10.1080/10426500701839882

2-(4-Fluorophenyl)methylidene-1-thiooxoindane-, 2-(4-methoxyphenyl) methylidene-1-thiooxoindane-, 2-(4-N,N-dimethyaminophenyl)methylidene-1- thiooxoindane dimers 5a-c were prepared by the reaction of the corresponding , -unsaturated ketones 3a-c with Lawe

Full text of DOI:10.1080/10426500701839882

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Phosphorus, Sulfur, and Silicon
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[4 + 2] Cycloaddition Reactions
Involving 2-Arylmethylidene-1-
thiooxoindan Intermediates
and Antimicrobial Activity
Evaluation of Some Products
Mohamed I. Hegab a , Tamer A. G. Elmalah a
Farouk A. Gad a
&
a Photochemistry Department , National Research
Centre , Dokki, Cairo, Egypt
Published online: 22 Jun 2009.
To cite this article: Mohamed I. Hegab , Tamer A. G. Elmalah & Farouk A.
Gad (2009) [4 + 2] Cycloaddition Reactions Involving 2-Arylmethylidene-1-
thiooxoindan Intermediates and Antimicrobial Activity Evaluation of Some Products,
Phosphorus, Sulfur, and Silicon and the Related Elements, 184:7, 1665-1675, DOI:
10.1080/10426500701839882
To link to this article: http://dx.doi.org/10.1080/10426500701839882
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Phosphorus, Sulfur, and Silicon, 184:1665–1675, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701839882
[4 + 2] Cycloaddition Reactions Involving
2-Arylmethylidene-1-thiooxoindan Intermediates and
Antimicrobial Activity Evaluation of Some Products
Mohamed I. Hegab, Tamer A. G. Elmalah,
and Farouk A. Gad
Photochemistry Department, National Research Centre, Dokki,
Cairo, Egypt
2-(4-Fluorophenyl)methylidene-1-thiooxoindane-, 2-(4-methoxyphenyl) methyli-
dene-1-thiooxoindane-, 2-(4-N,N-dimethyaminophenyl)methylidene-1-thiooxoin-
dane dimers 5a–c were prepared by the reaction of the corresponding α,β-
unsaturated ketones 3a–c with Lawesson’ Reagent (LR) in refluxing benzene. When
these dimers were refluxed with LR in xylene, the 1,2-thiaphospholene-2-sulfides
7a–c were obtained. On the other hand, the thermolysis of the dimers 5a–c in
the presence of acrylamide or dichloromaleic anhydride gave the corresponding
cycloadducts of Diels-Alder type 8a–c, and 10a–c, respectively. The 3-carbamoyl
thiapyran derivatives 8a–c showed good antimicrobial activity.
Keywords
Antimicrobial activity; 2-arylmethylidene-1-thiooxoindane dimers;
Diels–Alder cycloadducts; Lawesson’s reagent; 1,2-thiaphospholene-2-sulfides; α, β-
unsaturated ketones
INTRODUCTION
The α,β-unsaturated thiones are little known because of their instabil-
ity in the monomeric form1–9 and tendency to undergo [4 + 2] cycload-
dition in which the thione itself may serve as a dienophile or a diene.
However, Karakasa and Motoki10 reported the preparation of some
thiochalcone dimers and 2-arylbenzylidene-1-thiotetralone dimers via
the reaction of the corresponding α,β-unsaturated ketones with P4S10.
Also, the thermolysis of thiochalcone dimers and 2-arylbenzylidene-1-
thiotetralone dimers in the presence of acrylonitrile or acrylamide was
reported.10
Received 29 August 2007; accepted 18 September 2007.
The authors would like to thank Dr. Hassan M. Awad, Natural and Microbial Products
Department, National Research Centre, for the evaluation of the antimicrobial activity.
Address correspondence to Mohamed I. Hegab, Photochemistry Department, National
Research Centre, Dokki, 12622 Cairo, Egypt. E-mail: apmihegab65@yahoo.com
1665

1666
M. I. Hegab et al.
On the other hand, the reaction of some chalcones, 2-
arylbenzylidene-1-tetralones and 2,2-dialkyl-3-arylbenzylidene-4-chro-
manones with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiaphosphetane-
2,4-disulfide (Lawesson’s reagent, LR) was reported.11,12 Recently, some
new chromenothiapyran derivatives have been reported.13,14 In con-
tinuation of synthesis of some new thiapyran derivatives, it is in-
tended to explore the reaction of 2-arylbenzylidene-1-indanones with
LR in order not only to isolate the corresponding 2-arylbenzylidene-
1-thiooxoindanone dimers but also, to evaluate their antimicrobial
activities.
RESULTS AND DISCUSSION
In the present work, three known 2-arylbenzylidene-1-
indanones,
2-(4-methoxybenzylidene)indan-1-one
namely,
2-(4-fluorobenzylidene)indan-1-one
(3b), and
(3a),
2-(4-N, N
dimethylaminobenzylidene)indan-1-one (3c) were prepared according
to reference 15. Treatment of 2-(4-fluorobenzylidene)indan-1-one
(3a) with LR in refluxing benzene for 3h gave the corresponding
thiooxo dimmer 5a in moderate yield (Scheme 1). In this reaction,
the straightforward thionation of the carbonyl group of 3 yielded the
thiooxo monomer 4 which immediately underwent cyclization with
another thiooxo monomer [2 + 4] to yield the thiooxo dimer 5. The
structure of 5a was confirmed by analytical and spectral data. The
1H NMR spectrum of 5a showed one-proton singlets at 3.70 and
5.55 ppm; these were assigned to the C-4 and the C-2 protons in the
3,4-dihydro-2H-thiapyran ring, respectively. The mass spectrum of 5a
exhibited the molecular ion peak at 508 (M+, 2%) and a fragment from
the thiooxo monomer 4a (252, 100%, 4a+ – 2H) which would be formed
by the cleavage of 5a.
Similarly, 2-(4-methoxyphenyl)methylidene-1-thiooxoindan dimer
(5b) and 2-(4-N, N dimethylaminophenyl)methylidene-1-thiooxoindan
dimer (5c) were obtained by the reaction of 3b, and 3c with LR, respec-
tively (Scheme 1). The structures of 5b,c are supported by analytical
and spectral data (cf. Experimental).
However, when the thiooxo dimers 5a–c reacted with LR in reflux-
ing xylene for 6 h, the phosphorus containing compounds 7a–c, respec-
tively, were formed (Scheme 1).
The structures of phosphorus containing compounds 7a–c were con-
1
firmed by analytical and spectral data. The H NMR spectrum of 7a
showed the doublet at 5.39 ppm with JPH = 15 Hz due to the presence
of an adjacent CH moiety. Its mass spectrum showed the molecular ion
peak at 424 (M+, 12%), and a base peak at 391 (M+ – SH, 100%).

Arylmethylidene-1-thiooxoindan Intermediates
1667
SCHEME 1
On the other hand, the thermolysis of α,β-unsaturated thioxo dimers
5a–c in the presence of acrylamide in dry benzene for 1 h gave only
adducts which were identified as 8a–c based on 1H NMR (cf. Scheme 2).
In a competition reaction the unstable α,β-unsaturated thioxo monomer

1668
M. I. Hegab et al.
SCHEME 2
4 cyclized with an external dienophile rather than with itself. This
reaction proved the presence of an unstable α,β-unsaturated thioxo
monomer as the intermediate. The 1H NMR of 8a showed 4-CH at 5.54
ppm as a doublet with J = 3 Hz and 3-CH at 4.79–4.89 as a multiplet.
If derivative 9 would have formed, the 4-CH would appear as a triplet.
Thus, according to the 1H NMR data the compounds 9a–c could be
excluded. The IR spectrum of compound 8a showed bands at 3275,
2925 (NH2), and 1661 cm−1 (C=O).

Arylmethylidene-1-thiooxoindan Intermediates
1669
Products 8a–c show clearly the 1H NMR signals of only one diasteri-
omer. If the minor diasteriomer is present, its concentration too small
to be detected.
Similarly, the α,β-unsaturated thioxo dimers 5a–c were heated the
presence of dichloromaleic anhydride in dry xylene for 3 h to give
adducts 10a–c (cf. Scheme 2). The IR spectrum of compound 10a
showed bands at 1773, 1723 cm−1 [C(O)OC(O)]. Its 1H NMR spectrum
revealed a signal at 5.55 (1H, s, CH). The mass spectrum of compound
10a showed the molecular ion peak at 424 (M+ 2Cl37,1), 422 (M+ Cl37,35
,
9), and 420 (M+ 2Cl35, 50).
ANTIMICROBIAL ACTIVITY
The in vitro antimicrobial activity of the new synthesized thiapyran
derivatives was investigated against several pathogenic representa-
tive Gram-negative bacteria, Gram-positive bacteria, fungi, and yeast.
All microorganisms used were obtained from the culture collection of
the Department of Natural and Microbial Products, National Research
Centre, Dokki, Cairo, Egypt.
Medium16–18
The cap-assay method containing (g/L): peptone 6, yeast extract 3, meat
extract 1.5, glucose 1, and agar 20 was used. The medium was sterilized
and divided while hot (50–60◦C) in 15-mL portions among sterile 9-
cm diameter Petri dishes. One mL of the spore suspension of each
microorganism was spread all over the surface of the cold solid medium
placed in the Petri dish.
Method
0.5 g of each of the tested compounds was dissolved in 5 mL of N, N-
dimethylformamide, an amount of 0.1 mL of test solution was placed
on a 9-mm diameter Whatman paper disc, and the solvent was left
to evaporate. These saturated discs were placed carefully on the sur-
face of the incubated solid medium; each Petri dish contains at least
3 discs. The Petri dishes were incubated at 5◦C overnight, then exam-
ined. The results were then recorded by measuring the inhibition zone
diameters.

1670
M. I. Hegab et al.
TABLE I The Antimicrobial Activity of Some Newly Synthesized
Compounds
Inhibition zone (mm)
Microorganism
Bacteria
Gram-negative
Gram-positive
Fungi
Yeast
Tested
Compounds
and Standards
Escherichia
Coli
Bacillus
Subtilis
Aspergillus
Niger
Candida
Albicans
Streptomycin
Fusidic Acid
5a
5b
5c
8a
8b
8c
+++
—
—
—
—
+
+
+
—
—
—
+++
—
—
—
—
+
+
+
—
—
—
+
+++
—
—
—
—
—
—
—
—
—
+++
+++
++
+
+
+++
++
++
++
+
10a
10b
10c
+
+++ Highly sensitive (21–25 mm); ++ Fairly sensitive (16–20 mm); + Slightly
sensitive (15–10 mm); —Not sensitive.
RESULTS
The antimicrobial activity of the tested compounds (5a–c, 8a–c, and
10a–c) was evaluated by measuring the zone diameters and their
results were compared with those of well-known drugs as shown
in Table I. 3-Carbamoyl thiapyran derivatives 8a–c showed good
antimicrobial activity. However, 3-carbamoyl-4-(4-fluorophenyl)-2,3,4-
trihydroindeno[1,2-e]thiapyran (8a) demonstrated inhibitory activity
more than 8b and 8c.
EXPERIMENTAL
Melting points are uncorrected and recorded on a digital Electrother-
mal IA 9000 SERIES melting point apparatus (Electrothermal, Essex,
U.K.). Microanalyses were performed with all final compounds on
Elementar-Vario EL, Microanalytical Unit, Central Services Labora-
tory, National Research Centre, Cairo, Egypt. The 1H NMR spectra
were taken for samples in CDCl3 as solvent (unless otherwise men-
tioned) with Jeol EX-270 and Jeol EX-500 MHz NMR spectrometers,
Central Services Laboratory, National Research Centre, Cairo, Egypt.

Arylmethylidene-1-thiooxoindan Intermediates
1671
Chemical shifts are quoted in δ and were referenced to that of the sol-
vents. Splitting patterns were designated as follow: s singlet; d doublet;
t triplet; m multiplet. Mass spectra were recorded on Shimadzu GCMS-
QP 1000 EX EI (70 eV) spectrometers (Micro-Analytical Center of Cairo
University). IR spectra were obtained with Brucker-Vector 22 for KBr
wafers (Micro-analytical Center of Cairo University). Compounds 3a–
c15 were prepared according to the literature procedure.
Reaction of Arylbenzylidene-1-indanone Derivatives
3 with Lawesson’s Reagent (LR)
A mixture of 3 (2 mmol) and LR (0.4 g, 1.1 mmol) in dry benzene
(20 mL) was refluxed for 3 h. After cooling, the reaction mixture was
filtered off and the filtrate was evaporated. The residue was chro-
matographed on silica gel (Fluka 60, particle size 0.06–0.20 mm) using
diethyl ether:petroleum ether 40–60◦C 1:10 (v/v) as an eluent. The sol-
vent was evaporated and the residue was recrystallized from ethanol
to give thiapyran derivatives 5.
2,4-Di(4-fluorophenyl)spiroindan-2 ꢀ,3-inden[1,2-b]-2,4-
dihydrothiapyran-1 ꢀ-thione (5a)
From 3a (0.46 g). Green crystals, m.p. 223–226◦C, yield 55% (0.5 g).
IR: v = 2915, 1690, 1605, 1510, 1460, 1250, 1171, 1031, 835, 759, 715
1
cm−1. H NMR: δ = 3.44 (2H, s, CH2), 3.52 (2H, s, CH2), 3.70 (1H, s,
CH), 5.55 (1H, s, CH), 6.97–7.57 (16H, m, Ar-H). MS (EI): m/z (%) =
508 (M+, 2), 475 (24), 424 (2), 394 (5), 367 (15), 254 (29), 252 (100), 219
(9), 139 (43), 126 (19), 115 (15). Anal. calcd. for C32H22F2S2 (508.62): C,
75.56; H, 4.36; S, 12.60%. found: C, 75.34; H, 4.22; S, 12.29.
2,4-Di(4-metoxyphenyl)spiroindan-2 ꢀ,3-inden[1,2-b]-2,4-
dihydrothiapyran-1 ꢀ-thione (5b)
From 3b (0.50 g). Green crystals, m.p. 109–111◦C, yield 57% (0.57
g). IR: v = 2923, 1701, 1607, 1509, 1459, 1249, 1176, 1033, 833, 758,
717 cm−1. 1H NMR: δ = 3.43 (2H, s, CH2), 3.53 (2H, s, CH2), 3.70 (1H,
s, CH), 3.85 (6H, s, OCH3), 5.75 (1H, s, CH), 6.50–7.35 (16H, m, Ar-H).
MS (EI): m/z (%) = 266 (1/2M+, 74), 265 (100), 251 (29), 235 (53), 221
(22), 189 (20), 151 (44), 121 (25), 110 (8). Anal. calcd. for C34H28O2S2
(532.68): C, 76.65; H, 5.29; S, 12.03%. found: C, 76.34; H, 5.12; S, 11.79.
2,4-Di(4-N,N-dimethylaminophenyl)spiroindan-2 ꢀ,
3-inden[1,2-b]-2,4-dihydrothiapyran-1 ꢀ-thione (5c)
From 3c (0.52 g). Dark green crystals, m.p. 223–226◦C, yield 50%
(0.55 g). IR: v = 2918, 1610, 1586, 1569, 1521, 1465, 1323, 1265, 1162,

1672
M. I. Hegab et al.
1094, 1029, 947, 814, 758, 718 cm−1
.
1H NMR: δ = 2.84 (12H, s, 2
N(CH3)2), 3.43 (2H, s, CH2), 3.50 (2H, s, CH2), 3.71 (1H, s, CH), 5.65
(1H, s, CH), 6.70–7.85 (16H, m, Ar-H). MS (EI): m/z (%) = 279 (1/2M+,
61), 278 (100), 263 (11), 235 (21), 221 (2), 189 (3), 164 (49), 148 (17), 139
(25), 132 (14), 121 (17), 115 (14). Anal. calcd. for C36H34N2S2 (558.77):
C, 77.37; H, 6.13; N, 5.01%. found: C, 77.04; H, 5.98; N, 4.79.
Heating of Thioxo Dimers 5 with Lawesson’s Reagent (LR)
A mixture of 5 (2 mmol) and LR (0.8 g, 2.1 mmol) in dry xylene (20 mL)
was refluxed for 6 h. After cooling, the reaction mixture was filtered off
and the filtrate was evaporated. The residue was chromatographed
on silica gel (Fluka 60, particle size 0.06–0.20 mm) using diethyl
ether:petroleum ether 40–60◦C 1:10 (v/v) as an eluent. The solvent
was evaporated and the residue was recrystallized from ethanol to give
phosphorus compounds 7.
3-(4-Fluorophenyl)-2-(4-methoxyphenyl)indeno[1,2-d]-3H-1,2-
thiaphospholene-2-sulfide (7a)
From 5a (1.0 g). Colorless crystals, m.p. 201–204◦C, yield 60% (0.48
g). 1H NMR: δ = 3.51 (2H, s, CH2), 3.79 (3H, s, OCH3), 5.39 (1H, d, JPH
= 15Hz, 3-CH), 6.77–7.67 (12H, m, Ar-H). MS (EI): m/z (%) = 424 (M+,
12), 391 (100), 345 (50), 254 (29), 222 (19), 139 (33), 126 (29), 115 (16).
Anal. calcd. for C23H18FOPS2 (424.48): C, 65.07; H, 4.27; S, 15.10%.
found: C, 64.81; H, 4.07; S, 14.93.
2,3-Di(4-methoxyphenyl)indeno[1,2-d]-3H-1,2-
thiaphospholene-2-sulfide (7b)
From 5b (1.0 g). Colorless crystals, m.p. 91–94◦C, yield 63% (0.54 g).
1H NMR: δ = 3.50 (2H, s, CH2), 3.68 (3H, s, OCH3), 3.80 (3H, s, OCH3),
5.39 (1H, d, JPH = 15Hz, 3-CH), 6.77–7.67 (12H, m, Ar-H). MS (EI): m/z
(%) = 436 (M+, 12), 404 (100), 379 (50), 266 (19), 222 (39), 139 (23), 126
(19), 115 (15). Anal. calcd. for C24H21O2PS2 (436.52): C, 65.03; H, 4.85;
S, 14.68%. found: C, 64.85; H, 4.57; S, 14.43.
3-(4-N,N-Dimethylphenyl)-2-(4-methoxyphenyl)indeno[1,2-d]-
3H-1,2-thiaphospholene-2-sulfide (7c)
From 5c (1.1 g). Colorless crystals, m.p. 198–201◦C, yield 45%
1
(0.20 g). H NMR: δ = 2.86 (6H, s, N(CH3)2), 3.52 (2H, s, CH2), 3.81
(3H, s, OCH3), 5.40 (1H, d, JPH = 15Hz, 3-CH), 6.97–7.77 (12H, m,
Ar-H). MS (EI): m/z (%) = 449 (M+, 10), 416 (100), 279 (50), 221 (20),
139 (33), 126 (29). Anal. calcd. for C25H24NOPS2 (449.56): C, 66.78; H,
5.38; N, 3.11; S, 14.26%. found: C, 66.46; H, 5.19; N, 2.98; S, 14.03.

Arylmethylidene-1-thiooxoindan Intermediates
1673
The Thermolysis of α,β-unsaturated thioxo dimers 5
in the Presence of Acrylamide
A solution of α,β-unsaturated thioxo dimers 5 (1 mmol) and acrylamide
(0.15 g, 2.1 mmol) in dry benzene (10 mL) was refluxed for 1 h. The
solvent was evaporated and the residue was chromatographed on silica
gel (Fluka 60, particle size 0.06–0.20 mm) using petroleum ether 40–
60◦C as an eluent. The solvent was evaporated and the residue was
recrystallized from ethanol to give the adduct 8.
3-Carbamoyl-4-(4-fluorophenyl)-2,3,4-trihydroindeno[1,2-e]
thiapyran (8a)
From 5a (0.5 g). Colorless crystals, m.p. 108–110◦C, yield 30% (0.1
g). IR: v = 3275, 2925, 1661, 1625, 1515, 1464, 1250, 1173, 1031, 833,
1
761, 715 cm−1. H NMR: δ = 3.50 (2H, s, CH2), 3.85 (2H, d, J = 3Hz,
CH2), 4.79–4.89 (1H, m, CH), 5.45 (1H, d, J = 3Hz, CH), 5.85 (2H, br.
s, NH2), 6.95–7.35 (8H, m, Ar-H). MS (EI): m/z (%) = 325 (M+, 25), 254
(19), 235 (100), 189 (9), 118 (43). Anal. calcd. for C19H16FNOS (325.38):
C, 70.13; H, 4.95; N, 4.30; S, 9.85%. found: C, 69.84; H, 4.82; N, 4.18; S,
9.64.
3-Carbamoyl-4-(4-methoxyphenyl)-2,3,4-trihydroindeno
[1,2-e]thiapyran (8b)
From 5b (0.5 g). Colorless crystals, m.p. 65–68◦C, yield 38% (0.12
g). IR: v = 3275, 2926, 1665, 1627, 1515, 1462, 1250, 1171, 1031, 835,
763, 717 cm−1. 1H NMR: δ = 3.50 (2H, s, CH2), 3.83 (3H, s, OCH3), 3.86
(2H, d, J = 3Hz, CH2), 4.77–4.85 (1H, m, CH), 5.45 (1H, d, J = 3Hz,
CH), 5.84 (2H, br. s, NH2), 6.95–7.55 (8H, m, Ar-H). MS (EI): m/z (%)
= 337 (M+, 45), 266 (39), 235 (100), 189 (19), 118 (23). Anal. calcd. for
C20H19NO2S (337.41): C, 71.89; H, 5.67; N, 4.14; S, 9.50%. found: C,
71.54; H, 5.82; N, 3.88; S, 9.24.
3-Carbamoyl-4-(4-N,N-dimethylaminophenyl)-2,3,4-
trihydroindeno[1,2-e]thiapyran (8c)
From 5c (0.5 g). Colorless crystals, m.p. 112–115◦C, yield 32%
(0.11 g). IR: v = 3275, 2926, 1660, 1625, 1517, 1460, 1250, 1171, 1031,
1
837, 763, 715 cm−1. H NMR: δ = 2.85 (6H, s, N(CH3)2), 3.51 (2H, s,
CH2), 3.85 (2H, d, J = 3Hz, CH2), 4.78–4.87 (1H, m, CH), 5.45 (1H, d,
J = 3Hz, CH), 5.85 (2H, br. s, NH2), 6.95–7.55 (8H, m, Ar-H). MS (EI):
m/z (%) = 350 (M+, 15), 234 (100), 189 (29), 118 (14). Anal. calcd. for
C21H22N2OS (350.45): C, 71.96; H, 6.32; N, 7.99; S, 9.14%. found: C,
71.64; H, 6.22; N, 7.68; S, 8.84.

1674
M. I. Hegab et al.
The Thermolysis of α,β-unsaturated Thioxo Dimers 5
in the Presence of Dichloromaleic Anhydride
A solution of α,β-unsaturated thioxo dimers 5 (1 mmol) and dichloroma-
leic anhydride (3.32 g, 2.1 mmol) in dry xylene (10 mL) was refluxed for 3
h. The solvent was evaporated and the residue was chromatographed on
silica gel (Fluka 60, particle size 0.06–0.20 mm) using petroleum ether
40–60◦C as an eluent. The solvent was evaporated and the residue was
recrystallized from ethyl acetate to give the adduct 10.
3a,10a-Dichloro-10-(4-fluorophenyl)-3a,9,10,10a-
tetrahydroindeno[1,2-e]thiapyran[2,3-d]furan-1,3-dione (10a)
From 5a (0.5 g). Colorless crystals, m.p. 118–121◦C, yield 25% (0.2 g).
IR: v = 2925, 1773, 1723, 1606, 1511, 1463, 1250, 1177, 1032, 916, 834,
1
757 cm−1. H NMR: δ = 3.50 (2H, s, CH2), 5.55 (1H, s, CH), 6.95–7.55
(8H, m, Ar-H). MS (EI): m/z (%) = 424 (M+ 2Cl37, 1), 422 (M+ Cl37,35,9),
420 (M+ 2Cl35, 50), 350 (19), 306 (9), 235 (100), 189 (19), 152 (15). Anal.
calcd. for C20H11Cl2FO3S (421.26): C, 57.01; H, 2.63; S, 7.61%. found:
C, 56.88; H, 2.55; S, 7.34.
3a,10a-Dichloro-10-(4-methoxphenyl)-3a,9,10,10a-
tetrahydroindeno[1,2-e]thiapyran[2,3-d]furan-1,3-dione (10b)
From 5b (0.5 g). Colorless crystals, m.p. 78–81◦C, yield 27% (0.2 g).
IR: v = 2924, 1771, 1723, 1604, 1509, 1461, 1248, 1175, 1030, 915, 832,
755 cm−1. 1H NMR: δ = 3.50 (2H, s, CH2), 3.84 (3H, s, OCH3), 5.53 (1H,
s, CH), 6.97–7.58 (8H, m, Ar-H). MS (EI): m/z (%) = 436 (M+ 2Cl37, 2),
434 (M+ Cl37,35, 18), 432 (M+ 2Cl35, 50), 399 (3), 397 (15), 384 (100), 369
(20), 363 (4), 265 (49), 250 (12), 235 (20), 221 (8), 189 (8), 151 (19). Anal.
calcd. for C21H14Cl2O4S (433.29): C, 58.20; H, 3.25; S, 7.39%. found: C,
57.98; H, 3.05; S, 7.14.
3a,10a-Dichloro-10-(4-N,N-dimethylaminophenyl)-3a,9,10,10a-
tetrahydroindeno[1,2-e]thiapyran[2,3-d]furan-1,3-dione (10c)
From 5c (0.5 g). Colorless crystals, m.p. 123–125◦C, yield 25% (0.2
g). IR: v = 2924, 1775, 1725, 1606, 1507, 1465, 1248, 1175, 1030, 917,
1
832, 757 cm−1. H NMR: δ = 2.86 (6H, s, N(CH3)2), 3.52 (2H, s, CH2),
5.51 (1H, s, CH), 6.96–7.57 (8H, m, Ar-H). MS (EI): m/z (%) = 449 (M+
2Cl37, 2), 447 (M+ Cl37,35, 18), 445 (M+ 2Cl35, 50), 412 (3), 410 (16), 375
(10), 360 (5), 331 (39), 250 (15), 235 (21), 221 (7), 189 (10), 151 (20).
Anal. calcd. for C22H17Cl2NO3S (446.33): C, 59.19; H, 3.84; N, 3.13%.
found: C, 58.88; H, 3.65; N, 2.79.

Arylmethylidene-1-thiooxoindan Intermediates
1675
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