New crown compounds containing a 1,3,4-thiadiazole moiety: Synthesis and crystal structure

Article abstract of DOI:10.1002/jhet.170

(Chemical Equation Presented) The syntheses of new macrocyclic compounds are described. The 2,5-bis(hydroxyphenyl)-1,3,4-thiadiazole reacts with allyl bromide to give the corresponding allyloxy derivative. The allyl is used to functionalize the ortho posi

Full text of DOI:10.1002/jhet.170

November 2009
New Crown Compounds Containing a 1,3,4-Thiadiazole Moiety:
Synthesis and Crystal Structure
1119
Moha Outirite,a Fouad Bentiss,b Mounim Lebrini,a Jean-Pierre Wignacourt,a
a
and Michel Lagrenee *
´
a
´
Unite de Catalyse et de Chimie du Solide, CNRS UMR 8181, ENSCL, F-59652 Villeneuve
d’Ascq Cedex, France
Laboratoire de Chimie de Coordination et d’Analytique, Faculte des Sciences, Universite Chouaib
b
´
Doukkali, M-24000 El Jadida, Morocco
´
*E-mail: michel.lagrenee@ensc-lille.fr
Received January 21, 2009
DOI 10.1002/jhet.170
Published online 27 October 2009 in Wiley InterScience (www.interscience.wiley.com).
The syntheses of new macrocyclic compounds are described. The 2,5-bis(hydroxyphenyl)-1,3,4-thia-
diazole reacts with allyl bromide to give the corresponding allyloxy derivative. The allyl is used to
functionalize the ortho position by means of a Claisen rearrangement under microwave irradiation. New
2,5-dihydroxyphenyl-1,3,4-thiadiazoles are obtained, which are converted into macrocyclic polyethers.
1
The structures of the new macrocyclic compounds were confirmed by H, 13C NMR, and mass spectros-
copy. The crystal structure of 2,5-bis(2-allyloxyphenyl)-1,3,4-thiadiazole has been determined.
J. Heterocyclic Chem., 46, 1119 (2009).
INTRODUCTION
ing behaviors toward cations, water, and organic mole-
cules, such as amines or urea. Similar compounds such
as crown-annelated oligothiophenes have been previ-
ously used as model compounds for molecular actuation
[9]. In this work, the cation complexing properties were
In the field of supramolecular chemistry, crown ethers
(CEs) belong to the most popular hosts, because their
inclusion complexes have found a vast number of practi-
cal applications [1]. Growing interest has focused on the
construction of synthetic macrocyclic polyether com-
pounds containing heterocyclic subunits because these
compounds have been shown to possess great ability to
undergo selective complexation with charged as well as
neutral species [2–4]. Cation complexing properties of
synthetic macrocyclic polyether ligands containing a
heterocyclic subcyclic unit, such as pyridine, have been
previously studied by Bradshaw et al.þusingþcalorimetric
technique for the reaction of Naþ, K , Ag , NH4þ, and
Ba2þ [5]. Series of such compounds containing diaryl-
1,3,4-oxadiazoles and thiadiazoles have been reported
recently [6–8]. In light of the general interest on the
construction of synthetic macrocycles containing hetero-
cyclic subunits as well as limited example of 1,3,4-thia-
diazole inclusion in a macrocyclic framework, we report
in this article the synthesis of new macrocyclic poly-
ethers containing 2,5-diaryl-1,3,4-thiadiazole. These new
macrocyclic compounds are expected to show coordinat-
1
analyzed by H NMR titration experiments with solution
of Ba2þ, Sr2þ, or Pb2þ. More recently, the metal cation
complexing properties of crown-annelated oligothio-
phenes containing 3,4-ethylenedioxythiophene have been
studied showing that one of these compounds exhibit
interesting complexing properties for Pb2þ [10]. The
problem of recognition and selective binding of ions
occupies a prominent place in separation process, espe-
cially in radiochemical technologies. For example, the
extraction of uranium and of transuranium and rare-earth
metals from nitric acid solutions with various function-
ally substituted CEs has been investigated by Yakshin
et al. [11]. Recently, some macrocyclic polyether com-
pounds containing a 1,3,4-thiadiazole moiety have been
used as corrosion inhibitors for mild steel in acidic media
[12]. The existing data show that most organic inhibitors
act by adsorption on the metal surface [13], and it was
discovered that the corrosion inhibition may be enhanced
C
V
2009 HeteroCorporation

´
M. Outirite, F. Bentiss, M. Lebrini, J.-P. Wignacourt, and M. Lagrenee
1120
Vol 46
Scheme 1
by various chemicals additives such as cation salts. Mac-
rocyclic derivatives with potential complexing properties
are expected to be useful for this purpose.
the two OH groups, which implies the rotation of the
two oxygen atoms to the sulfur side as previously calcu-
lated [8]. After evaporation of the solvent in vacuo, the
solid residue is treated with a solution of sodium hydrox-
ide. The 2,5-bis-(2-allyloxyphenyl)-1,3,4-thiadiazole 2
was collected by filtration, washed with water, and
recrystallized from ethanol. The structure proposed for
this new thiadiazole derivative is consistent with the data
RESULTS AND DISCUSSION
The 2,5-bis (2-hydroxyphenyl)-1,3,4-thiadiazole
1
1
reacts with allyl bromide in the presence of solid potas-
sium carbonate suspended in acetone. The mixture is
heated under reflux during 12 h. The end of the reaction
is controlled by TLC (thin layer chromatography) using
a 50/50 mixture of ethylacetate and petroleum ether as
eluent. Under these experimental conditions, the reaction
takes place in basic media to allow the deprotonation of
obtained from their H, 13C, MS, and elemental analysis.
Single crystals suitable for X-ray diffraction study
were obtained by slow evaporation of ethanol, and the
crystal structure of compound 2 was investigated
(Scheme 1).
The main features of the crystal structure of 2 are
resulting from the quasi planarity of the whole entity:
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

November 2009
New Crown Compounds Containing a 1,3,4-Thiadiazole Moiety:
Synthesis and Crystal Structure
1121
tion; a second set with a similar alternating organization
of planar entities parallel to the [10-1] axis is seen at
about c/2. This new ligand with sulfur and two p bonds
is offering soft ligation sites and the two oxygen atoms
provide hard ligation sites, all five of which are pointed
toward a single space and are likely to discriminate
between potential metals.
The allyl group was used to functionalize the ortho
position to the phenol by means of a Claisen rearrange-
ment. The compound 2 was exposed to microwave irra-
diation in ethylene glycol at an elevated temperature
(200ꢀC). This reaction was conducted under microwave
heating to improve the yield and the purity of the prod-
uct. The double bond of the allyl substituent was iso-
merized into conjugation with the aryl under basic con-
ditions using potassium tert-butoxide [14].
Figure 1. Projection view of compound 2.
only O2, C10, C11, C18, and C20 are out of the mean
plane containing most of the molecule; when using the
central thiadiazole ring as planar reference, the phenyl
ring on the right (C3 to C8, Fig. 1) is tilted 2ꢀ anticlock-
wise, whereas the other phenyl ring (C12 to C17) is
tilted clockwise of 4ꢀ. The structure is described by
stacking two different layers of such 2 entities along the
[001] direction: a first set, located in the (001) basal
plane of the unit cell, is seen with molecules of 2 with
their central thiadiazole ring pointing upward and down-
ward alternatively, stacked parallel to the [101] direc-
EXPERIMENTAL
Melting points were determined on an IA 9000 series elec-
trothermal apparatus and are uncorrected. Elemental analyses
of C, H, N, and S were performed at the Elemental Analysis
1
service of CNRS, Vernaison, France. H and 13C NMR spectra
were recorded on a Bruker F.T. AC 300 spectrometer (300
Table 2
˚
Bond distances (A) and angles (°) for compound 2.
˚
Bond distances (A)
Table 1
S1AC1
S1AC2
C1AN1
C1AC8
N1AN2
C2AN2
C2AC12
C3AO2
C3AC4
C4AC5
C5AC6
C7AC6
C8AC3
C8AC7
1.727(1)
1.724(1)
1.316(1)
1.470(1)
1.363(1)
1.314(1)
1.471(1)
1.360(1)
1.398(1)
1.385(2)
1.388(2)
1.385(2)
1.402(1)
1.402(1)
C9AC10
C9AO2
1.484(2)
1.432(1)
1.306(2)
1.402(1)
1.407(1)
1.363(1)
1.398(1)
1.381(2)
1.386(2)
1.388(2)
1.441(1)
1.317(2)
1.487(2)
Summary of the crystal data and structure refinement
C10AC11
C12AC17
C12AC13
C13AO1
C13AC14
C14AC15
C15AC16
C17AC16
C18AO1
C19AC20
C19AC18
for compound 2.
Formula
C20 H18 N2 O2 S
350.42 g/mol
Monoclinic
Formula weight
Crystal system
Space group
P 21/n
˚
a (A)
a ¼ 7.6640(2)
b ¼ 16.0490(5)
c ¼ 14.2818(4)
˚
b (A)
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
b ¼ 95.8
3
˚
V (A )
1747.6(4)
Angles (ꢀ)
Z
4
1.33
296
736
Dcal (mg/m3)
T (K)
F(000)
C2AS1AC1
C1AN1AN2
C2AN2AN1
N1AC1AC8
N1AC1AS1
C8AC1AS1
N2AC2AC12
N2AC2AS1
C12AC2AS1
O2AC3AC4
O2AC3AC8
C4AC3AC8
C3AC4AC5
C4AC5AC6
C6AC7AC8
C3AC8AC7
87.82(4)
113.0(1)
113.2(1)
120.2(1)
113.0(1)
126.8(1)
120.3(1)
113.0(1)
126.6(1)
123.7(1)
115.7(1)
120.5(1)
119.7(1)
120.8(1)
121.4(1)
118.2(1)
C3AC8AC1
C7AC8AC1
O2AC9AC10
122.9(1)
118.9(1)
108.1(1)
118.4(1)
118.7(1)
122.9(1)
123.7(1)
115.9(1)
120.3(1)
119.8(1)
120.9(1)
119.6(1)
121.0(1)
108.0(1)
123.5(1)
Crystal size, mm
l (mmꢂ1
Data collection range
Range of indices
0.1 ꢁ 0.1 ꢁ 0.1
C17AC12AC13
C17AC12AC2
C13AC12AC2
O1AC13AC14
O1AC13AC12
C14AC13AC12
C15AC14AC13
C14AC15AC16
C15AC16AC17
C16AC17AC12
O1AC18AC19
C20AC19AC18
)
0.201
k, ꢂ12 to 12; h,
ꢂ26 to 26; l, ꢂ23 to 23
Reflections measured
Rint
(Rall; R2r
(wRall; wR2r
Goodness of fit
Number of parameters
8482
3.91
)
5.99; 4.24
11.93; 10.77
1.02
)
298
0.44
ꢂ0.28
3
˚
Maximum peak in final DF map (e/A )
3
˚
Minimum peak in final DF map (e/A )
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

´
M. Outirite, F. Bentiss, M. Lebrini, J.-P. Wignacourt, and M. Lagrenee
1122
Vol 46
Scheme 2
MHz for 1H NMR and 75 MHz for 13C NMR) using chloro-
form (CDCl3) solvent. Matrix-assisted laser desorption ioniza-
tion (MALDI) and time-of-flight mass spectrometry (TOF-MS)
are used to record the mass spectra of the correspondent com-
pounds. All starting materials were of reagent grade and used
as purchased.
(100 mL) was added to dilute the solvent. The reaction mix-
ture was filtered. The resulting residue was recrystallized from
ethanol: mp 150–152ꢀC; yield 82%; 1H NMR (CDCl3) d
(ppm) 11.40 (s, 2H, OH); 7.41 (d, J ¼ 7.8 Hz, 2H), 7.29 (d,
A single crystal of compound 2 was mounted on a Brucker
AXS SMART three-circle diffractometer using graphite mono-
Table 3
Atomic coordinates and equivalent displacement for compound 2.
˚
chromated MoKa radiation (k ¼ 0.71073 A), equipped with a
2
CCD two-dimensional detector [15]. Data (Table 1) were cor-
rected for Lorentz, polarization, background, and decomposi-
tion effects. Atomic positions were determined using SHELXS
[16] and refined using full-matrix least-squares [17]. Hydrogen
positions were calculated and included in the final cycles of
refinement in constrained positions and with fixed isotropic
thermal parameters. Absorption corrections were not made
because of the small value of the absorption coefficients (Table
1). Extinction was refined for all three structures but was mini-
mal. Table 2 presents the bond angles and distances for com-
pound 2. The atomic coordinates and the equivalent displace-
ment are given in Table 3. The anisotropic displacement pa-
rameters for compound 2 are presented in Table 4.
˚
Atom
x/a
y/b
z/c
U (A )
S1
N1
N2
C1
C2
C3
0.35157(3)
0.3082(1)
0.2275(1)
0.3798(1)
0.2383(1)
0.5449(1)
0.6399(1)
0.6617(1)
0.5910(2)
0.4993(1)
0.4750(1)
0.5977(1)
0.5423(2)
0.5414(2)
0.1556(1)
0.1644(1)
0.0828(1)
ꢂ0.0078(1)
ꢂ0.0198(1)
0.0620(1)
0.2491(1)
0.3599(1)
0.3049(2)
0.2557(1)
0.5126(1)
0.453(2)
0.07961(1) 0.54044(1) 0.01935(5)
0.1719(1)
0.0984(1)
0.1723(1)
0.0433(1)
0.2526(1)
0.3231(1)
0.3882(1)
0.3840(1)
0.3135(1)
0.2464(1)
0.1867(1)
0.1106(1)
0.1046(1)
ꢂ0.0390(1)
ꢂ0.1009(1)
ꢂ0.1779(1)
ꢂ0.1931(1)
ꢂ0.1328(1)
ꢂ0.0564(1)
ꢂ0.1369(1)
ꢂ0.1018(1)
ꢂ0.0918(1)
0.3948(1)
0.3696(1)
0.4825(1)
0.4381(1)
0.6152(1)
0.6472(1)
0.5857(1)
0.4924(1)
0.4607(1)
0.5209(1)
0.7651(1)
0.8132(1)
0.9043(1)
0.4234(1)
0.4935(1)
0.4755(1)
0.3886(1)
0.3188(1)
0.3362(1)
0.6552(1)
0.7373(1)
0.8210(1)
0.0298(2)
0.0298(2)
0.0217(1)
0.0221(1)
0.0237(2)
0.0307(2)
0.0371(2)
0.0393(2)
0.0317(2)
0.0230(1)
0.0303(2)
0.0472(3)
0.0486(3)
0.0248(2)
0.0266(2)
0.0353(2)
0.0405(3)
0.0412(3)
0.0331(2)
0.0327(2)
0.0357(2)
0.0453(3)
0.0284(1)
0.0275(1)
0.040(4)
0.051(5)
0.046(4)
0.036(4)
0.049(4)
0.041(4)
0.090(7)
0.079(6)
0.072(6)
0.038(4)
0.050(4)
0.050(4)
0.051(4)
0.041(4)
0.040(4)
0.047(4)
0.068(6)
0.047(4)
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
O1
General procedure for the synthesis of compounds
1–7. The formula of the parent compounds with corresponding
numbers to carbons scheme is given later (Scheme 2).
Synthesis of 2,5-Bis(2-hydroxyphenyl)-1,3,4-thiadiazole
(1). Experimental method is reported in the literature [18].
Synthesis of 2,5-Bis(2-allyloxyphenyl)-1,3,4-thiadiazole
(2). A mixture of 2,5-bis(2-hydroxyphenyl)-1,3,4-thiadiazole 1
(0.02 mol), anhydrous potassium carbonate (10 g), and allyl
bromide (0.04 mol) in acetonitrile (100 mL) was heated under
reflux for 12 h with vigorous stirring. The solvent was evapo-
rated in vacuo, and the solid residue was heated under reflux
with 200 mL of a molar potassium hydroxide solution for 1 h.
After cooling, the crude product was filtered, washed with
water, and recrystallized from ethanol. Pale yellow solids were
obtained: mp 130ꢀC; yield 89%; 1H NMR (CDCl3) d (ppm)
8.39 (d, J ¼ 8.9 Hz, 2H); 7.54 (t, J ¼ 8.9 Hz, 2H), 7.30 (d,
J ¼ 7.5 Hz, 2H); 7.17 (t, J ¼ 7.5 Hz, 2H), 6.20 (m, 2H); 5.53
(d, Jtrans ¼ 18 Hz, 2H), 5.36 (d, Jcis ¼ 9.5 Hz, 2H); 4.84 (d,
J ¼ 6.1 Hz, 4H); 13C NMR (CDCl3) d (ppm) C1 162.68; C2
119.17; C3 155.05; C4 119.30; C5 132.63; C6 121.80; C7
128.21; C8 70.21; C9 133.42; C10 113.89. MALDI-TOFMS:
m/z 351 (M þ 1). Anal. Calcd. for C20H18N2O2S: C, 68.55; H,
5.18; N, 7.99; S, 9.15. Found: C, 68.20; H, 5.20; N, 8.06; S,
9.09.
ꢂ0.08041(4) 0.5773(1)
O2
H1
0.18688(4) 0.6711(0)
0.308(1)
0.429(1)
0.437(1)
0.326(1)
0.187(1)
0.237(1)
0.065(1)
0.1556(1)
0.055(1)
0.395(1)
0.451(1)
0.608(1)
0.708(1)
0.761(1)
0.797(1)
0.771(2)
0.944(1)
0.929(1)
0.291(1)
0.261(1)
0.379(1)
0.523(1)
0.635(1)
0.667(1)
0.728(1)
0.875(1)
0.833(1)
H2
H3
H4
H5
H6
H7
H8
H9
0.601(2)
0.728(2)
0.686(2)
0.724(2)
0.562(2)
0.519(3)
0.568(3)
0.502(3)
0.052(2)
H10
H11
H12
H13
H14
H15
H16
H17
H18
ꢂ0.014(1)
ꢂ0.142(1)
ꢂ0.246(1)
ꢂ0.222(1)
ꢂ0.193(1)
ꢂ0.142(1)
ꢂ0.091(1)
ꢂ0.072(1)
ꢂ0.104(1)
ꢂ0.085(2)
ꢂ0.065(2)
0.097(2)
0.293(2)
0.125(2)
Synthesis of 2,5-Bis[3-allyl-2-hydroxy)phenyl]-1,3,4-thia-
(3). 2,5-Bis(2-allyloxyphenyl)-1,3,4-thiadiazole
0.480(2)
0.383(3)
0.184(2)
diazole
2
(0.01 mol) was placed in multimode microwave and irradiated
for 1 h (300 W) at 200ꢀC in ethylene glycol (40 mL). Water
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

November 2009
New Crown Compounds Containing a 1,3,4-Thiadiazole Moiety:
Synthesis and Crystal Structure
1123
Table 4
Anisotropic displacement parameters for compound 2.
U11
U22
U33
U12
U13
U23
S1
N1
0.0197(1)
0.0307(4)
0.0299(4)
0.0202(3)
0.0184(3)
0.0219(3)
0.0285(4)
0.0351(5)
0.0395(5)
0.0310(4)
0.0212(3)
0.0308(4)
0.0710(9)
0.0705(9)
0.0190(3)
0.0185(3)
0.0238(4)
0.0276(4)
0.0303(5)
0.0271(4)
0.0281(4)
0.0274(4)
0.0462(6)
0.0249(3)
0.0329(3)
0.0198(1)
0.0340(4)
0.0368(4)
0.0239(4)
0.0274(4)
0.0228(4)
0.0278(4)
0.0262(5)
0.0268(5)
0.0278(5)
0.0213(4)
0.0388(5)
0.0432(7)
0.0474(7)
0.0282(4)
0.0231(4)
0.0246(4)
0.0353(6)
0.0528(7)
0.0447(6)
0.0253(4)
0.0366(5)
0.0464(7)
0.0239(3)
0.0274(3)
0.0184(1)
0.0237(3)
0.0219(3)
0.0209(3)
0.0209(3)
0.0269(4)
0.0367(5)
0.0514(7)
0.0525(7)
0.0366(5)
0.0267(4)
0.0209(4)
0.0249(5)
0.0277(5)
0.0279(4)
0.0388(5)
0.0587(7)
0.0604(8)
0.0419(6)
0.0284(4)
0.0450(6)
0.0426(6)
0.0432(7)
0.0358(4)
0.0215(3)
0.0020(1)
ꢂ0.0045(3)
ꢂ0.0052(3)
0.0018(3)
0.0016(1)
ꢂ0.0028(3)
ꢂ0.0018(3)
0.0021(3)
0.0029(3)
0.0053(3)
0.0080(4)
0.0117(5)
0.0095(5)
0.0039(4)
0.0037(3)
0.0014(3)
ꢂ0.0069(5)
0.0047(5)
0.0055(3)
0.0055(3)
0.0090(4)
0.0138(5)
0.0105(4)
0.0069(3)
0.0058(4)
0.0014(4)
0.0047(5)
ꢂ0.0003(3)
ꢂ0.0016(2)
0.0013(1)
0.0078(3)
0.0034(3)
N2
C1
0.0044(3)
C2
C3
C4
C5
C6
C7
C8
C9
0.0009(3)
0.0007(3)
ꢂ0.0016(3)
ꢂ0.0016(3)
ꢂ0.0081(4)
ꢂ0.0050(4)
0.0090(5)
ꢂ0.0042(3)
ꢂ0.0074(4)
ꢂ0.0048(4)
ꢂ0.0011(4)
0.0015(3)
0.0096(4)
0.0030(3)
ꢂ0.0037(4)
ꢂ0.0145(6)
0.0009(7)
ꢂ0.0036(4)
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
O1
0.0030(5)
0.0061(5)
0.0005(3)
0.0017(3)
ꢂ0.0078(3)
ꢂ0.0049(4)
ꢂ0.0083(4)
ꢂ0.0237(5)
ꢂ0.0272(5)
ꢂ0.0135(4)
0.0119(4)
ꢂ0.0008(3)
ꢂ0.0052(4)
ꢂ0.0086(5)
ꢂ0.0033(4)
0.0003(3)
ꢂ0.0006(4)
ꢂ0.0087(5)
ꢂ0.0026(2)
ꢂ0.0054(3)
0.0177(5)
0.0154(5)
0.0062(3)
ꢂ0.0001(2)
O2
J ¼ 7.8 Hz, 2H); 6.94 (t, J ¼ 7.8 Hz, 2H), 6.07 (m, 2H); 5.17
(d, Jtrans ¼ 17 Hz, 2H), 5.12 (d, Jcis ¼ 9.8 Hz, 2H); 3.54 (d,
J ¼ 6.8 Hz, 4H); 13C NMR (CDCl3) d (ppm) C1 165.90; C2
120.92; C3 153.52; C4 127.20; C5 133.28; C6 116.60; C7
128.84; C8 34.05; C9 136.72; C10 116.60. MALDI-TOFMS:
m/z 351 (M þ 1). Anal. Calcd. for C20H18N2O2S: C, 68.55; H,
5.18; N, 7.99; S, 9.15. Found: C, 68.33; H, 5.14; N, 8.02; S,
9.14.
Synthesis of 2,5-Bis[2-hydroxy-3-trans-1-propenyl)phenyl]-
1,3,4-thiadiazole (4). A suspension of potassium tert-butoxide
(8.40 g, 75 mmol) in acetonitrile (40 mL) was heated at 120ꢀC
under stirring until it was completely dissolved. 2,5-Bis[3-
allyl-2-hydroxy)phenyl]-1,3,4-thiadiazole 3 (7.5 mmol) was
added and stirring was continued for 10 min. The solvent was
evaporated. The residue was treated and recrystallized from
ethanol: mp 172ꢀC; yield 61%; 1H NMR (CDCl3) d (ppm)
11.36 (s, 2H, OH); 7.87 (d, J ¼ 7.6 Hz, 2H), 7.52 (d, J ¼ 7.6
Hz, 2H); 6.95 (t, J ¼ 7.6 Hz, 2H), 6.82 (d, J ¼ 16 Hz, 2H),
6.35 (m, 2H); 1.81 (d, J ¼ 6.8 Hz, 6H); 13C NMR (CDCl3) d
(ppm) C1 169.98; C2 118.42; C3 157.35; C4 130.27; C5
135.53; C6 121.20; C7 133.92; C8 132.15; C9 125.79; C10
18.95. MALDI-TOFMS: m/z 351 (M þ 1). Anal. Calcd. for
C20H18N2O2S: C, 68.55; H, 5.18; N, 7.99; S, 9.15. Found: C,
68.30; H, 5.27; N, 7.83; S, 9.11.
The solvent was evaporated in vacuo and the solid residue was
heated under reflux with 200 mL of a potassium hydroxide so-
lution for 1 h. After cooling, the crude product was filtered,
washed with water, and recrystallized from ethanol.
Macrocycle 5. mp 85ꢀC; yield 31%; 8.28 (d, J ¼ 7.8 Hz,
2H), 7.42 (t, J ¼ 7.8 Hz, 2H), 7.32 (d, J ¼ 7.8 Hz, 2H), 6.04
(m, 2H), 5.14 (t, J ¼ 17 Hz, 4H); 4.02 (m, 4H), 3.88 (m, 4H),
3.52 (s, 4H); 3.33 (d, J ¼ 6.0 Hz, 4H). 13C NMR (CDCl3) d
(ppm) C1 163.72; C2 116.24; C3 154.43; C4 73.98; C5 69.77;
C6 71.48; C12 130.74; C13 126.12; C14 131.18; C15 125.93;
C16 34.23; C17 135.42.51; C18 117.79. MALDI-TOFMS: m/z
465 (M þ 1). Anal. Calcd. for C26H28N2O4S: C, 67.24; H,
6.07; N, 6.03; S, 6.90. Found: C, 67.11; H, 6.08; N, 5.94; S,
6.88.
Macrocycle 6. mp 128ꢀC; yield 27%; 8.44 (d, J ¼ 7.8 Hz,
2H), 7.85 (t, J ¼ 7.8 Hz, 2H), 7.28 (d, J ¼ 7.8 Hz, 2H), 6.85
(d, J ¼ 16 Hz, 2H), 6.04 (m, 2H); 4.10 (m, 4H), 3.93 (m, 4H),
3.56 (s, 4H); 1.78 (d, J ¼ 6.8 Hz, 6H). 13C NMR (CDCl3) d
(ppm) C1 167.41; C2 117.27; C3 156.43; C4 74.84; C5 69.30;
C6 71.33; C12 133.81; C13 125.35; C14 134.18; C15 126.63;
C16 137.11; C17 124.51; C18 18.83. MALDI-TOFMS: m/z
465 (M þ 1). Anal. Calcd. for C26H28N2O4S: C, 67.24; H,
6.07; N, 6.03; S, 6.90. Found: C, 67.09; H, 6.03; N, 5.98; S,
6.82.
General procedure for the synthesis of macrocycles (5)
and (6). A mixture of 2,5-bis[3-allyl-2-hydroxy)phenyl]-1,3,4-
thiadiazole 3 or 3,5-bis[2-hydroxy-3-trans-1-propenyl)phenyl]-
1,3,4-thiadiazole 4 (5 mmol), anhydrous potassium carbonate
(24 mmol), and ethylene or polyethylene glycol ditosylate
(5 mmol) in 150 mL of nonprotic polar solvent (acetone, ace-
tonitrile, etc.) was irradiated in multimode microwave for 9 h.
Synthesis of macrocycle (7). A suspension of macrocyclic
compound 6 (1 g, 2.15 mmol) in boiling water (100 mL) was
prepared, to which sodium carbonate crystals (0.5 g) were
added, and 4 g of finely powdered potassium permanganate
(4 g) was slowly introduced. The mixture was heated under
reflux until the purple color of the permanganate disappeared
(1–4 h). After cooling, the mixture was filtered to remove any
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

´
M. Outirite, F. Bentiss, M. Lebrini, J.-P. Wignacourt, and M. Lagrenee
1124
Vol 46
[5] Bradshaw, J. S.; Maas, G. E.; Lamb, J. D.; Izatt, R. M.;
Christensen, J. J. J Am Chem Soc 1980, 16, 467.
excess of manganese dioxide and carefully acidified with
hydrochloride acid. The crude product was filtered, washed
with water, and recrystallized from ethanol. mp 258ꢀC; yield
47%; 11.31 (s, OH, 2H), 7.57 (d, J ¼ 7.8 Hz, 2H), 7.11 (d,
J ¼ 7.8 Hz, 2H), 6.98 (t, J ¼ 16 Hz, 2H); 4.15 (m, 4H), 3.58
(s, 4H). 13C NMR (CDCl3) d (ppm) C1 167.77; C2 117.27; C3
157.11; C4 72.52; C5 69.43; C6 72.01; C12 134.6; C13
127.16; C14 135.75; C15 127.12; C16 163.67. MALDI-
TOFMS: m/z 473 (M þ 1). Anal. Calcd. for C22H20N2O8S: C,
55.93; H, 4.27; N, 5.93; S, 6.79. Found: C, 56.10; H, 4.30; N,
6.06; S, 6.74.
[6] Zhou, J. M.; Hua, W. T.; Yang, Q. C. Gaodeng Xuexiao
Huaxue Xuebao 1996, 17, 1721.
´
[7] Bentiss, F.; Lebrini, M.; Lagrenee, M. J Heterocycl Chem
2004, 41, 419.
[8] Lebrini, M.; Bentiss, F.; Vezin, H.; Wignacourt, J. P.; Rous-
´
sel, P.; Lagrenee, M. Heterocycles 2005, 65, 2847.
[9] Jousselme, B.; Blanchard, P.; Levillain, E.; Delaunay, J.;
Allain, M.; Richomme, P.; Rondeau, D.; Gallego-Planas, N.; Roncalli,
J. J Am Chem Soc 2003, 125, 1363.
[10] Demeter, D.; Blanchard, P.; Allain, M.; Grosu, I.; Roncalli,
J. J Org Chem 2007, 72, 5285.
Acknowledgments. The authors acknowledge Frederic Capet
(CNRS research staff) for handling the X-ray data collection and
treatment for compound 2.
[11] Yakshin, V. V.; Pribylova, G. A.; Atamas, L. I.; Vilkova,
O. M.; Tananaev, I. G.; Tsivadze, A. Yu.; Myasoedov, B. F. Radio-
chemistry 2006, 48, 472.
´
[12] Lebrini, M.; Lagrenee, M.; Vezin, H.; Traisnel M.; Bentiss,
F. Corros Sci 2007, 49, 2254.
[13] Schmitt, G. Br Corros J 1984, 19, 165.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet