Thiafulvenes and thiafulvalenes in organic chemistry: Synthesis and study its behavior towards some chemical reagents

Article abstract of DOI:10.1080/10426500701407730

Trithiafulvenes were prepared through cycloaddition of 3-thioxo-1,2- dithioles to several electrophilic alkenes and alkynes. Treatments of the product with phenyl-hydrazine and malononitrile afforded the hydrazone and the dinitrilene derivatives respectiv

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Phosphorus, Sulfur, and Silicon
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Thiafulvenes and
Thiafulvalenes in Organic
Chemistry: Synthesis and Study
its Behavior towards Some
Chemical Reagents
Salem E. Zayed a , M. Ezel-Dean Hassan b & Rawia
Ragab c
a Facutly Science, Chemistry Department, South
Valley University, Qena, Egypt
b Faculty of Education, Chemistry Department, Suez
Canal University, Port Said
c Egyptian Sugar & Integrated Industries Company
(ESIIC), Industrial Production Affairs, Hawamdea,
Egypt
Available online: 16 Jul 2007
To cite this article: Salem E. Zayed, M. Ezel-Dean Hassan & Rawia Ragab (2007):
Thiafulvenes and Thiafulvalenes in Organic Chemistry: Synthesis and Study its
Behavior towards Some Chemical Reagents, Phosphorus, Sulfur, and Silicon and the
Related Elements, 182:9, 2205-2216
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Phosphorus, Sulfur, and Silicon, 182:2205–2216, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701407730
Thiafulvenes and Thiafulvalenes in Organic Chemistry:
Synthesis and Study its Behavior towards Some
Chemical Reagents
Salem E. Zayed
South Valley University, Facutly Science, Chemistry Department,
Qena, Egypt
M. Ezel-Dean Hassan
Suez Canal University, Faculty of Education, Chemistry Department,
Port Said
Rawia Ragab
Egyptian Sugar & Integrated Industries Company (ESIIC), Industrial
Production Affairs, Hawamdea, Egypt
Trithiafulvenes were prepared through cycloaddition of 3-thioxo-1,2-dithioles to
several electrophilic alkenes and alkynes. Treatments of the product with phenyl-
hydrazine and malononitrile afforded the hydrazone and the dinitrilene derivatives
respectively. The bromination and subsequent treatment with KCN and malonon-
itrile afforded the diene derivative. The aniline derivative was also obtained by
treatment with chloroaniline.
Keywords Sulfur heterocycles; tetrathiafulvalenes; thiafulvalenes; trithiafulvenes
INTRODUCTION
Trithiafulvenes and tetrathiafulvalenes were found to possess wide
applications in the fields of organic metals and superconductors,1
supramolecular chemistry,2 molecular scale electronic and optical
components,3 biological activities,4 reaction catalysis,5 and as diagnos-
tic and therapeutic agents6 and sensors.7
Owing to the foregoing knowledges, the authors tried to synthesize
some new heterocyclic compounds in the hope of obtaining some an-
timicrobial agents. The prepared compounds were examined to stop or
at least delate the growth of the harmful microorganisms that infect
Received February 3, 2006; accepted April 2, 2007.
Address correspondence to Salem Zayed, South Valley University, Faculty Science,
Chemistry Department, Qena 83523, Egypt. E-mail: zayedse@yahoo.com
2205

2206
S. E. Zayed et al.
sugar industry and cause damages to sucrose molecule and great loss
in sugar production.
Starting with α-oxoketen-gemdithioles (1) and (2), the trithiones (3)
and (4) could be prepared through sulfurization of (1) and (2) with
phosphorous pentasulfide.8−10 The common key step for the synthe-
sis of 1,3-dithiole-2-ylidenes (8,9) and 1,3-dithiolane-2-ylidene (10) is
the Diel’s-Alder cycloaddition of 3-thioxo-1,2-dithioles (3) and (4) to
an electrophilic alkynes,11 e.g., diethylacetylenedi-carboxylate (5) and
acetylenedicarboxyolic acid (6) or alkenes,12 e.g., maleic acid (7) in
methylene chloride (Scheme 1).
SCHEME 1
Formation of the products (8–9) is suggested to proceed as follows:
Structure of the product (10) was confirmed chemically via reacting
(4) with maleic anhydride (11) in boiling xylene followed by alkaline hy-
drolysis and acidification of the product (12) to give the diacid derivative
(13), which was found to be identical with (10). Furthermore, boiling the
anhydride (12) in ethanol containing few drops of sulfuric acid resulted
in anhydride ring opening and the diester derivative (14) was formed.

Thiafulvenes and Thiafulvalenes in Organic Chemistry
2207
Formation of the anhydride (12) was assumed to proceed via 1,3-dipolar
cycloaddition reaction (Scheme 2).
SCHEME 2
Trithiafulvenes (8) and (9) when allowed to react with phenylhy-
drazine (2 mole) in methylene chloride gave a title compounds of the

2208
S. E. Zayed et al.
types (15) and (16). 1HNMR spectra for (15 and 16) indicates the pres-
ence of both [CO NH NH Ph] and C N NH Ph moieties, while the
peak for thione group disappeared.
1,3-Dithiole-2-ylidene is a strong donor group,13 so, the hydrogen
atom attached at C2 is available for replacement. As a result, bromina-
tion of (16) proceeded smoothly yielding the bromo-derivative (17).
Furthermore, reaction of trithiafulvene (8) with malononitrile re-
sulted in the formation of product (18). Malononitrile was added to
the thione group instead of ethylenic double bond and finally hydro-
gen sulfide was detected. Spectral measurements proved the presence
of proton located at C2 and IR spectra shows a peak corresponding to
cyano groups.
Addition reaction to trithiafulvene (8) was investigated. On reduction
of (8) with Na/EtOH, the reduced product (19) was obtained. Formation
of (19) was confirmed by 1HNMR spectra where a newly methylene and
thiole protons were detected.
Moreover, treatment of the substrate (9) with bromine formed the
substitution reaction product (20). Structure of (20) was proved via the

Thiafulvenes and Thiafulvalenes in Organic Chemistry
2209
disappearance of the signal characteristic of the proton at C2. Stirring
the product (20) with potassium cyanide in aqueous ethanol favored
substitution of bromine atom by cyanide moiety and finally the product
(21) was gathered (Scheme 3).
Consequently, by treating the diacid trithiafulvene derivative (21)
with malononitrile in boiling absolute ethanol in presence of triethy-
lamine, the reaction takes place towards addition to cyano group form-
ing a dieno-structure (22) (Scheme 3).
SCHEME 3
The reaction of substrate (20) with aromatic amines, e.g., p-
chloroaniline (23) in boiling ethanol containing catalytic amount of

2210
S. E. Zayed et al.
triethylamine, led to the formation of product (24) via a debromina-
tion addition reaction. The structure of (24) was proved by spectral and
analytical measurements.
EXPERIMENTAL SECTION
Elemental analysis: were carried out at Microanalytical Unit, Cairo
University Mass spectra: were obtained on a GCMS-QP 1000 EX mass
Spectrometer with ionization potential of 70 eV and a Mass Spectrom-
eter MS 30 MS9 (AEI) at 70 eV. IR spectra: were determined with a
Shimadzu IR 408 Infrared Spectrophotometer using KBr wafer tech-
1
nique. H-NMR: carried out on Varian EM 390 (300 MHz) using TMS
as internal standard and chemical shifts are expressed as ppm (δ).
Melting points: All melting points are uncorrected and were deter-
mined either on a sulfuric acid apparatus or on a Kofler melting point
apparatus.
Synthesis of Dithioles (1) and (2)—General Procedure
Carbondisulfide (0.60 ml; 0.01 mol) was added to (0.01 mol) acetylth-
iophene or acetylfuran in dry benzene (150 ml) and the mixture
was cooled to 0–5◦C. Potassium tertiary butoxide (2.8 g; 0.025 mol)
was added gradually to the cooled mixture with continuous shak-
ing. Cold water was then added with continuous shaking and the
benzene layer was separated. The aqueous layer was washed sev-
eral times with petroleum ether 40/60. The aqueous layer was cooled
and gradually acidified with concentrated sulfuric acid. The sepa-
rated precipitate was filtered off and recrystallized from benzene to
give:
1) thiole (1) from acetylthiophene as red crystals, m.p. 83◦C.(yield
89.21%) Elemental analysis: C7H6OS3,M.wt 202.298 Calc.:C
41.56,H 2.99,S 47.54 Found:C 41.60,H 3.0, S 47.56; and

Thiafulvenes and Thiafulvalenes in Organic Chemistry
2211
2) thiole (2) from acetylfuran as yellowish-brown crystals, m.p. 50◦C.
(yield 78.93%). Elemental analysis: C7H6O2S2, M.wt 186.238 Calc.:C
45.14,H 3.25,S 34.43 Found:C 45.11,H 3.25,S 34.40.
Synthesis of 1,2-dithiacyclopentene-3-thiones (3)
and (4)—General Procedure
To the dithiole 1 or 2 (0.01 mol) in dry benzene (100 ml) was added
phosphorouspentasulfide (0.15 mol). The reaction mixture was heated
on a water bath for 5 h, and then filtered while hot. The clear benzene
layer was concentrated to its half volume followed by addition of appro-
priate quantity of petroleum ether 40/60. The precipitated solid product
was filtered off and washed twice with petroleum ether 40/60 giving the
required thione (3) or (4).
1) Dithiole (1) gave 1,2-dithiole-3-thione (3) as reddish-brown crys-
tals from methylene chloride, m.p. 118◦C, (yield 78.74%). Elemen-
tal analysis: C7H4S4, M.wt 216.342 Calc.:C 38.86,H 1.86,S 59.28
Found:,C 39.01,H 1.82,S 60.02
2) Dithiole (2) gave 1,2-dithiole-3-thione (4) as brown crystals from
methylene chloride, m.p. 110◦C, (yield 86.34%). Elemental analy-
sis: C7H4OS3,M.wt 200.282 Calc.:C 41.98, H 2.01,S 48.02 Found:C
42.01,H 2.00,S 48.03
Synthesis of 1,3-Dithiole-2-ylidene Systems (8), (9) and (10)
Diethyl-2-(2-Thien-2-yl-2-thioxoethylidene)-1,3-dithiole-4,5-
dicarboxylate (8)
A mixture of dithiolethione 3 (2.16 g; 0.01 mol) and diethylacetylene-
dicarboxylate 5 (1.5 ml; 0.01 mol) was stirred in methylene chlo-
ride (30 ml) at room temperature for 3 h. The solvent was left
to evaporate at room temperature, and the formed precipitate was
recrystallized from diethylether as violet crystals, m.p. 105◦C in
quantitative yield (89.63%). Elemental analysis: C15H14O4S4, M.wt
386.502 Calc.:C 46.61,H 3.65,S 33.18 Found:C 46.66,H 3.66, S
33.08.
2-[2-(2-Furyl)-2-thioxoethylidene]-1,3-dithiole-4,5-dicarboxylic
Acid (9)
A mixture of dithiolethione 4 (2.0 g; 0.01 mol) and acetylenedicar-
boxylic acid 6 (1.14 ml; 0.01 mol) was stirred in methylene chloride
(30 ml) at room temperature for 3 h. The solvent was left to evap-
orate at room temperature and the formed precipitate was gathered

2212
S. E. Zayed et al.
and recrystallized from ethanol as dark brown crystals, m.p. 165◦C,
(yield 92.62%). Elemental analysis: C11H6O5S3 ,M.wt 314.338 Calc.:C
42.03,H 1.92, S 30.60 Found:C 42.15,H 1.89,S 30.52 IR (KBr): ν (cm−1):
1720 ( C O), 1170 ( C S), 2700 ( OH) of carboxyl, 1480 (>C CH).
2-[2-(2-Furyl)-2-thioxoethylidene]-1,3-dithiolane-4,5-di-
carboxylic Acid (10)
A mixture of dithiolethione 4 (2.0 g; 0.01 mol) and maleic acid 7 (1.16
ml; 0.01 mol) was stirred in methylene chloride (20 ml) at room temper-
ature for 2 h. The solvent was left to evaporate at room temperature and
the product was collected and recrystallized from dioxane as reddish-
brown crystals, m.p. 240◦C in quantitative yield ( 93.21%). Elemen-
tal analysis: C11H8O5S3 , M.wt 316.354 Calc.: C 41.76,H 2.55, S 30.40
Found:C 41.87,H 2.52,S 30.35 IR (KBr): ν (cm−1): 1720 ( C O), 1170
1
( C S), 2700 ( OH) of carboxyl, 1480 (>C CH). H-NMR (DMSO): δ
(ppm): 7.46–7.78 (m, 3H, furan), 8.04 (s, 1H, C CH), 6.64-6.84 (s, 2H,
C4-C5-1,3-dithole).
Synthesis of 2-[2-(2-Furyl)-2-thioxoethylidene]dihydro[1,3]
dithiolo[4,5-c]furan-4,5-dione (12)
Dithiolethione 4 (2.0 g; 0.01 mol) was refluxed with maleic anhydride
11 (0.98 g; 0.01 mol) in xylene (15 ml) for 2 h. The reaction mixture was
concentrated, cooled and the formed precipitate was filtered off and
recrystallized from ethanol as deep violet crystals, m.p. 180◦C in quan-
titative yield, (88.95%). Elemental analysis: C11H6O4S3 , M.wt 298.338
Calc.:C 44.28,H 2.03,S 32.24 Found:C 44.43,H 2.04,S 32.33.IR (KBr): ν
1
(cm−1): 1090 ( C S), 1480 (C CH). H-NMR (DMSO): δ (ppm): 7.34–
7.69 (m, 3H, furan), 8.34 (s, 1H, C CH), 6.62–6.64 (s, 1H, C4), 6.25–6.28
(s, 1H, C5, C4-C5-1,3-dithiole).
Synthesis of 2-[2-(2-Furyl)-2-thioxoethylidene]-1,3-dithiolane-
4,5-dicarboxylic Acid (13)
The anhydride derivative 12 (2.98 g; 0.01 mol) was stirred with hot
aqueous potassium hydroxide (2 g KOH/25 ml H2O) for 1 h. The re-
action mixture was acidified with concentrated hydrochloric acid and
the formed precipitate was filtered off and recrystallized from diox-
ane as brown crystals, m.p. 240◦C, (yield 71.26%). Elemental analysis:
C11H8O5S3 , M.wt 316.354 Calc.: C 41.76, H 2.55, S 30.40; Found: C
41.86,H 2.00,S 30.37. IR (KBr): ν (cm−1): 1720 ( C O), 1170 ( C S),
1
2700 ( OH) of carboxyl, 1480 (>C CH). H-NMR (DMSO): δ (ppm):
7.46-7.78 (m, 3H, furan), 8.04 (s, 1H, C CH), 6.64-6.84 (s, 2H, C4-C5-
1,3-dithiole).

Thiafulvenes and Thiafulvalenes in Organic Chemistry
2213
Synthesis of Diethyl 2-[2-(2-Furyl)-2-thioxoethylidene]-1,3-
dithiolane-4,5-dicarboxylate (14)
The anhydride 12 (2.98 g; 0.01 mol) was boiled in ethanol (25 ml) con-
taining sulfuric acid (1 ml) for 5 h. The diester derivative (14) was
obtained after neutralization with alkali. The separated solid product
was filtered off and recrsytallized from ethanol as orange crystals, m.p.
150◦C, (yield 69.22%). Elemental analysis: C15H16O5S3 , M.wt 372.458
Calc.:C 48.37,H 4.33, S 25.82 Found: C 48.52,H 4.32, S 25.88 IR (KBr):
ν (cm−1): 1540 ( COO−), 1050 (C S), 1490 ( CH2), 1410, 1380 ( CH3).
1H-NMR (DMSO): δ (ppm): 8.1–8.11 (s, 1H, C CH), 1.24 (t, 6H, 2CH3
ester), 3.35 (s, 4H, 2CH2 ester), 6.83-6.85 (s, 2H, C4-C5 cyclic, 1,3-
dithiacyclopent.), 7.58-7.71 (m, 3H, furan).
5-(N-Phenylhydrazinocarbonyl)-2-(2-phenylhydrazino)-2-
thiophene-2-yl-ethylidene-1,3-dithiole (15)
Obtained from (8) as a pale yellow crystals from methylene chloride,
m.p. 240◦C, (yield 60.37%.) Elemental analysis: C25H22N4O3S3 ,M.wt
522.638 Calc.:C 57.45, H 4.24, N 10.72, S 18.40 Found:C 57.49,H 4.18,N
10.75, S 18.38 IR (KBr): ν (cm−1): 1730 (C O), 3000 ( CH), 1640
( CONH), 1490 ( CH2), 1390 ( CH3), 750 (5H adj.). 1H-NMR (DMSO):
δ (ppm): 8.3 (s, 1H, C CH), 6.75–7.04 (m, 10H, 2C6H5), 7.6 (s, 1H,
N NH), 7.12–7.22 (m, 3H, thiophene), 8.1 (s, 1H, CONH), 7.32 (q, 2H,
CH2), 7.43 (s, 3H, CH3).
(2E)-2-[2-(2-Furyl)-2-(2-phenylhydrazino]-N-phenyl-1,3-
dithiole-4-carboxylic Acid-3-carbohydrazide (16)
Obtained from (9) as a brownish-orange crystals from dioxane, m.p.
80◦C, (yield 60.81%). Elemental analysis: C23H18N4O4S2 ,M.wt 478.526
Calc.:C 57.73,H 3.79,N 11.71,S 13.40 Found:,C 57.76,H 3.77,N 11.73 S
13.37 IR (KBr): ν (cm−1): 1715 (C=O), 750 (5H, adj), 2700 ( OH) of
carboxyl, 1640 ( CONH).
Synthesis of (2E)-2-[1-bromo-2-(-2-furyl)-2-phenylhydrazino]-
1,3-dithiole-4-carboxylic acid-3-carbohydrazide (17)
A mixture of 16 (4.78 g; 0.01 mol) in chloroform (20 ml) and bromine
(0.96 ml; 0.01 mol) in chloroform (10 ml) was stirred in direct sunlight
for 2 h. The solvent was left to evaporate at room temperature and
the product was collected and recrystallized from methylene chloride
as dark brown crystals, m.p. 205◦C, (yield 82.81%). Elemental analysis:
C23H17BrN4O4S2, M.wt 557.43 Calc.:C 49.55 H 3.07, N 10.05, S 11.50
Found:C 49.74 H 3.05, N 10.09, S 11.49

2214
S. E. Zayed et al.
Synthesis of Diethyl-2-(3,3-Dicyano-2-thien-2-yl-prop-2-eny-
lidene-1,3-dithiole-4,5-dicarboxylate (18)
A mixture of trithiafulvene 8 (3.86 g; 0.01 mol) and malononitrile (0.78
ml; 0.01 mol) was heated under reflux in absolute ethanol (30 ml) for 3 h
in the presence of few drops of triethylamine. The reaction mixture was
concentrated, cooled and acidified with dilute hydrochloric acid. The
formed precipitate was filtered off and recrystallized from ethanol as
brown crystals in quantitative (yield (96.11%), m.p. 150◦C. Elemental
analysis: C18H14N2O4S3, M.wt 418.488 Calc.: C 51.66, H 3.37,N 6.69,S
22.98 Found:C 51.95,H 3.38,N 6.74, S 22.95 IR (KBr): ν (cm−1): 1540
( COO−), 1735 ( C O), 2500 ( CN), 1650 ( C C ). 1H-NMR (DMSO):
δ (ppm): 1.23 (t, 2CH3), 3.89-3.98 (q, 2CH2), 7.22-7.95 (m, 3H, thio-
phene), 8.15 (s, 1H, C CH).
Synthesis of Diethyl 2-(2-mercapto-2-thien-2-yl-ethyl)-1,3-
dithiole-4,5-dicarboxylate (19)
Small pieces of sodium metal (0.03 mol) were added gradually while
stirring at room temperature to trithiafulvene (8) (0.01 mol, 3.865 g)
in absolute ethanol (20 ml). The formed brown precipitate was filtered
off and recrsytallized from ethanol, m.p. 220◦C, (yield 77.13%). Ele-
mental analysis:C15H18O4S4 M.wt 390.534 Calc.:C 46.13,H 4.65,S 32.84
Found:C 46.09, H 4.60,S 32.84 IR (KBr): ν (cm−1): 1355 ( COO ), 1475
( CH2), 2850 ( SH), 1735 ( C O). 1H-NMR (DMSO): δ (ppm): 1.23 (t,
3H, ester), 2.51-2.52 (s, CH2-), 8.1 (s, 1H, CH), 7.18–7.84 (m, 3H,
thiophene), 3.65 (q, CH2-ester), 8.71 (s, 1H, CH CH2), 1.44 (s,1H
SH).
Synthesis of 2-[1-Bromo-2-(2-furyl)-2-thioxoethylidene]-1,3-
dithiole-4,5-dicarboxylic Acid (20)
A mixture of trithiafulvene 9 (3.14 g; 0.01 mol) in chloroform (20 ml) ,and
bromine (0.96 ml; 0.01 mol) in chloroform (10 ml) was stirred in direct
sunlight for 2 h. The solvent was left to evaporate at room temperature.
Product (20) was collected and recrsytallized from methanol in the form
of light brown crsytals, shrinking at 145◦C, (yield 80.42%) . Elemental
analysis: C11H5BrO5S3 , M.wt 393.246. Calc.:C 33.59,H 1.28,Br 20.32,S
24.46 Found:C 33.92,H 1.30, Br 21.00, S 24.47 IR (KBr): ν (cm−1): 2700
( OH) of carboxyl, 1200 ( C S), 1720 ( C O)

Thiafulvenes and Thiafulvalenes in Organic Chemistry
2215
Synthesis of 2-[1-Cyano-2-(2-furyl)-2-thioxoethylidene]-1,3-
dithiole-4,5-dicarboxylic Acid (21)
To the bromo derivative 20 (3.93 g; 0.01 mol) in ethanol (20 ml), aque-
ous potassium cyanide (0.65 g; 0.01 mol) was added. The mixture was
stirred at room temperature for 3 h. After cooling, the solid prod-
uct so formed was collected and recrystallized from dioxane to give a
dark brown crystals, m.p. >250◦C, (yield 30.37%). Elemental analysis:
C12H5NO5S3 , M/wt 339.348. Calc.: C 42.47, H 1.49, N 4.13, S 28.34
Found:C 42.47, H 1.47, N 4.09, S 28.38. IR (KBr): ν (cm−1): 2800 ( OH)
of carboxyl, 2100 ( CN), 1710 ( C O), 1120 ( C S), 1600 (C C).
Synthesis of 2-[2-Amino-3,3-dicyano-1-(2-furylcarbono-
thioyl)prop-2-enylidene]-1,3-dithiole-4,5-dicarboxylic Acid (22)
A mixture of the cyano derivatives 21 (4.19 g; 0.01 mol) and malnonitrile
(0.78 g; 0.01 mol) in ethanol (30 ml) containing catalytic amount of tri-
ethylamine (0.3 ml) was refluxed for 4 h. The solvent was concentrated
and the remaining was cooled. The formed precipitate was filtered off
and recrystallized from dioxane, m.p. >250◦C, yield 80%. Elemental
analysis: C15H7N3O5S3 , M/wt 405.41. Calc.: C 44.44, H 1.74, N 10.37,
S 23.72 Found:C 44.49,H 1.75,N 10.35, S 23.68 IR (KBr): ν (cm−1): 2210
(-CN), 1710 ( C O), 3335 ( NH2), 2800 ( OH) of carboxyl, 1020 (C S),
1650 ( C C ).
Synthesis of 1-[(4-Chlorophenyl)amino]-2-(2-furyl)-2-thioxo-
ethylidene]-1,3-dithiole-4,5-dicarboxylic Acid (24)
A mixture of the bromo derivative 20 (3.93 g; 0.01 mol) and p-
chloroaniline 23 (1.27 g; 0.01 mol) in ethanol (50 ml) containing cat-
alytic amount of triethylamine (0.3 ml) was refluxed for 5 h. The re-
action mixture was concentrated, cooled and the formed precipitate
was filtered off, washed with water and recrsytallized from dioxane as
deep green crystals, m.p. 220◦C, (yield 60.27%%). Elemental analysis:
C17H10ClNO5S3, M/wt 439.895 Calc.: C 46.41, H 2.29. N 3.18, S 21.86
Found:C 46.45, H 2.28,N 3.18, S 21.83.
REFERENCES
[1] S. Kumara, H. Kurai, T. Mori, and S. Tanaka, Bull. Chem. Soc. Jpn, 74, 59 (2001).
[2] (a) J. Becher and K. Schaumberg, Ed. Molecular Engineering for Advanced Mate-
rials, (Kluwer Academic: Dordrecht, 1994) NATO ASI Series; (b) T. Jÿrgensen, T.K.
Hansen and Becher, J. Chem. Soc. Rev., 41, (1994); (c) M. Adam and K. Mullen, Adv.
Mat., 6, 439 (1994).

2216
S. E. Zayed et al.
[3] (a) A. Aviram, Ed., Molecular Electronics—Science and Technology; United Engi-
neering Trustees, Inc., 1989; (b) J.-M. Lehn, Angew. Chem., Int. Ed. Engl., 27, 89–
112 (1988); (c) J.-M. Lehn, Angew. Chem., Int. Ed. Engl., 29, 1304–1319 (1990).
[4] K. M. Kadish, K. M. Smith, and R. Guilard, Eds, The Porphyrin Handbook, (Aca-
demic Press, San Diego, 2000).
[5] M. L. Merlau, M. P. Mejia, S. T. Ngugen, and J. T. Hupp, Angew. Chem. Int. Ed., 40,
4239 (2001).
[6] T. D. Mody and J. L. Sessler, In Supramolecular Materials and Technologies, D. N.
Reinhoudt, Ed. (Wiley, Chichester, 1999) Ch.7.
[7] J. M. Pedrosa, C. M. Dooling, T. H. Richardson, R. K. Hyde, C. A. Hunter, M. T.
Martin, and L. Camacho, J. Mater. Chem., 12, 2659 (2002).
[8] R. R. Rastogi, H. Ila, and H. Junjappa, J.C.S. Chem. Commun., 645 (1975).
[9] R. R. Rastogi, A. Kumar, H. Iia, and H. Junjappa, J.C.S. Perkin I, 554–558 (1975).
[10] M. Saquet and A. Thuillier, Bull. Soc. Chim., 1183 (1966).
[11] (a) H. Behringer, D. Bender, J. Falkenberg, and R. Wiedenmann, Chem. Ber., 101,
1428–1444 (1968); (b) D. M. McKinnon and J. M. Buchsriber, Can. J. Chem., 49,
3299–3304 (1971); (c) H. Davy, J. Vialle, J. Bull. Soc. Chim., Fr., 1435–1436 (1975).
[12] R. Csuk and B. I. Glonzer, Comprehensive Heterocyclic Chemistry (1982–1995), Ch.
3.12, p. 648.
[13] R. Gompper, H.-U. Wagner, and E. Kutter, Chem. Ber., 101, 4123 (1968).