2120
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Fedorov et al.
Tunable Absorbance Detector and Waters 996 Photodiode Arꢀ
ray Detector, PDA) using the Millennium 32 software and on a
Beckman instrument (System Gold 125 solvent module, System
Gold 168 detector, PDA, System Gold 125s solvent module,
and System Gold 166 detector) using the Beckman System Gold
Chromatography Software 1991 (System Gold Personal Chroꢀ
matograph). The separation was carried out on reversedꢀphase
columns (Symmetry C18, Waters, 3.9×150 mm, 5 µm; Beckman
Ultrasphere, 4.6×250 mm; Beckman Ultrasphere, 2.0×250 mm,
5 µm) using a MeCN—H2O mixture as the eluent.
Experimental
Magnesium, calcium, barium, sodium, potassium, rubidium,
and cesium perchlorates were dried in vacuo at 230 °C. Spectroꢀ
scopicꢀgrade acetonitrile containing less than 0.005% water
(Aldrich) was used without additional purification.
All experiments, including the preparation of solutions of
ligand 2, were carried out under red light. Potassium tertꢀbutoxꢀ
ide was prepared by dissolution of potassium metal in anhydrous
ButOH followed by evaporation of excess ButOH and drying
in vacuo. Nꢀ(3ꢀAcetylaminophenyl)acetamide,24,25 Nꢀ(3ꢀthioꢀ
acetylaminophenyl)thioacetamide,24,25 and 2,7ꢀdimethylbenꢀ
zo[1,2ꢀd;3,4ꢀd´]bisthiazole24,25 were synthesized according to
procedures described earlier.
Elemental analysis was carried out in the Laboratory of
Microanalysis of the A. N. Nesmeyanov Institute of Organoꢀ
element Compounds of the Russian Academy of Sciences
(Moscow). The melting points (uncorrected) were measured on
an Melꢀtemp II instrument.
The 1H NMR spectra were recorded in CD3CN at 30 °C on
a Bruker DRXꢀ500 spectrometer (500.13 MHz). The chemical
shifts and the coupling constants were measured with an accuꢀ
racy of 0.01 ppm and 0.1 Hz, respectively.
The mass spectra were obtained on a Varian MAT 311A
instrument using a direct inlet system; the ionization energy
was 70 eV. The electrospray mass spectra (electrospray ionizaꢀ
tion, ESI method) and highꢀresolution mass spectra were meaꢀ
sured on a JEOL AccuTOF JMSꢀT100LC mass spectrometer.
The electronic absorption spectra were recorded on a
Specord M40 spectrophotometer connected to a computer. The
fluorescence spectra were measured on Shimadzu RFꢀ5000
spectrofluorimeter at 20 1 °C. The fluorescence quantum yields
of the ligand and its complexes were determined at 20 1 °C for
airꢀsaturated acetonitrile solutions with respect to quinine sulꢀ
fate in 0.5 M H2SO4 as the reference (ϕF = 0.55). The excitation
wavelength of 365 nm was used. The quantum yields were calcuꢀ
lated using uncorrected fluorescence spectra.
Complexation of E,Eꢀ2 with Mg, Ca, Ba, Na, K, and Rb
perchlorates was studied by spectrophotometric titration at
20 1 °C by varying the concentration of the corresponding perꢀ
chlorate at a constant concentration of the ligand. The comꢀ
plexation constants and absorption spectra of the complexes
were calculated from the electronic absorption spectra of soluꢀ
tions using the HYPERQUAD program.26
Acetonitrile solutions of compound 2 and its complexes were
irradiated using a mercury lamp (DRKꢀ120, 120 W). The lines
with wavelengths λ = 313, 365, and 405 nm were separated using
UFSꢀ2 + ZhSꢀ3, UFSꢀ6 + BSꢀ7, and PSꢀ13 + ZhSꢀ10 glass
light filters, respectively, from a standard kit of optical stained
glasses. The light intensity was measured using a ferrioxalate
actinometer.
The course of the synthesis was monitored by TLC on
DCꢀAlufolien Kieselgel 60 F254 and DCꢀAlufolien Aluminiumꢀ
oxid 60 F254 neutral (Type E) plates. Column chromatography
was performed on Kieselgel 60 (0.063—0.100 mm) and alumiꢀ
num oxide 150, basic, Type E (0.063—0.200 mm), and aluꢀ
minium oxide 90 active, neutral (activity 1) (0.063—0.200 mm)
(Merck).
2,5ꢀDimethylbenzo[1,2ꢀd;3,4ꢀd´]bisthiazole (4). A solution
of 1,3ꢀbis(thioacetylamido)benzene (3.1 g, 13.8 mmol) and
NaOH (9.5 g, 237.5 mmol) in water (150 mL) was mixed with a
solution of K3[Fe(CN)6] (18.7 g, 56.8 mmol) in water (200 mL).
The reaction mixture was kept with continuous stirring at ~20 °C
for 3 days. The reaction product was isolated by repeated extracꢀ
tion with diethyl ether. The ethereal extract was washed with a
large amount of water and concentrated. Compound 4 was obꢀ
tained in a yield of 0.43 g (8%), m.p. 93 °C (cf. lit. data24,25
92—94 °C).
:
5ꢀMethylꢀ2ꢀ[2ꢀ(E)ꢀ(2,3,5,6,8,9,11,12ꢀoctahydroꢀ
1,4,7,10,13ꢀpentaoxabenzocyclopentadecynꢀ15ꢀyl)ethenꢀ1ꢀ
yl]benzo[1,2ꢀd;3,4ꢀd´]bisthiazole (3) and 2,5ꢀbis[2ꢀ(E)ꢀ
(2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀpentaoxabenzocycloꢀ
pentadecynꢀ15ꢀyl)ethenꢀ1ꢀyl]benzo[1,2ꢀd;3,4ꢀd´]bisthiazole
(E,Eꢀ2). A mixture of bisthiazole 4 (44 mg, 0.2 mmol),
4´ꢀformylbenzoꢀ15ꢀcrownꢀ5 ether (130 mg, 0.44 mmol), and
ButOK (49 mg, 0.67 mmol) in anhydrous DMSO (10 mL) was
kept at room temperature for 24 h. Then water (20 mL) was
added, the products were extracted with chloroform, the solvent
was evaporated, and the residue was chromatographed on Al2O3
(aluminium oxide 150 basic, type T). After recrystallization from
MeCN, compound 3 was obtained in a yield of 5 mg (5%), m.p.
212 °C. Found (%): C, 60.14; H, 5.84; N, 5.31. C25H26N2O5S2.
Calculated (%): C, 60.22; H, 5.26; N, 5.61. 1H NMR, δ: 3.60
(m, 8 H, 4 OCH2); 3.95 and 4.50 (both m, 4 H each, 4 OCH2);
7.08 (d, 1 H, H(5´), J = 7.5 Hz); 7.37 (d, 1 H, H(6´), J =
7.6 Hz); 7.45 (s, 1 H, H(2´)); 7.60 (d, 1 H, Ha, 3JH,H = 16.1 Hz);
3
7.69 (d, 1 H, Hb, JH,H = 16.1 Hz); 7.95 (d, 1 H, H(8), J =
8.6 Hz); 8.19 (d, 1 H, H(7), J = 8.6 Hz).
The yield of E,Eꢀ2 was 28 mg (18%), m.p. 162 °C.
Found (%): C, 61.74; H, 5.84; N, 3.71. C40H44N2O10S2. Calcuꢀ
lated (%): C, 61.84; H, 5.71; N, 3.61. 1H NMR, δ: 3.60 (m,
16 H, 8 OCH2); 3.95 (m, 8 H, 4 OCH2); 4.50 (m, 8 H, 4 OCH2);
7.01 (d, 2 H, H(5´), H(5″), J = 8.5 Hz); 7.31 and 7.33 (both d,
1 H each, H(6´), H(6″), J = 8.4 Hz, J = 8.4 Hz); 7.46 and 7.49
(both s, 1 H each, H(2´), H(2″)); 7.58 and 7.69 (both d, 2 H each,
3
3
H , H , H , H , J = 16.1 Hz, JH,H = 16.1 Hz); 7.92
″
″
b
a´
a
b´
H,H
(d, 1 H, H(8), J = 8.6); 8.18 (d, 1 H, H(7), J = 8.6 Hz). MS,
m/z: 776 [M]+ (100), 500 (87), 224 (13), 184(14), 144 (24), 125
(21), 114 (20), 77 (15), 58 (45), 51 (27). MS of a solution of
ligand E,Eꢀ2 in MeCN (ESI, 2 kV, 250 °C, 0.2 mL min–1),
m/z: 799.3 [(E,Eꢀ2)•Na]+, 1575.6 [2(E,Eꢀ2)•Na]+, 1591.6
[2(E,Eꢀ2)•K]+.
Solutions of the complexes of ligand E,Eꢀ2 with Mg and Ba
perchlorates in MeCN. A solution of ligand 2 (2.4•10–5 mol L–1
)
in MeCN was prepared by diluting its concentrated solution
(7.54•10–5 mol L–1). A solution of Mg(ClO4)2 (1•10–2 mol L–1
)
in MeCN (4.8 µL) was added to a solution of 2 (C = 2.4•10–5
mol L–1) in MeCN (2 mL) to prepare predominantly the comꢀ
plex of 1 : 1 composition (ligand : cation), or a solution of
Studies by HPLC were carried out on a Waters instrument
(Waters 600 Controller, Waters 600/616S Pump, Waters 486