bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis...
Transcript of bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4 ... · S1 Supporting Information for Synthesis...
S1
Supporting Information
for
Synthesis of new, highly luminescent bis(2,2’-
bithiophen-5-yl) substituted 1,3,4-oxadiazole, 1,3,4-
thiadiazole and 1,2,4-triazole
Anastasia S. Kostyuchenko1,2, Vyacheslav L.Yurpalov1, Aleksandra Kurowska3,
Wojciech Domagala3, Adam Pron4 and Alexander S. Fisyuk*1,2
Address: 1Department of Organic Chemistry, Omsk F. M. Dostoevsky State University,
55a Mira Ave, 644077 Omsk, Russia, 2Laboratory of New Organic Materials, Omsk
State Technical University, Mira Ave, 11, Omsk 644050, Russia, 3Department of
Physical Chemistry and Technology of Polymers, Silesian University of Technology,
Marcina Strzody 9, 44-100 Gliwice, Poland and 4Faculty of Chemistry Warsaw
University of Technology, Noakowskiego 3, 00-664 Warszawa, Poland
* Corresponding author
Email: Alexander S. Fisyuk - [email protected]
Experimental part
Table of Contents
General information.................................................................................................S2
Experimental procedures and analytical data..........................................................S3
References……………………………………………………………………………….S11
S2
General information
The IR spectra were recorded on an Infralum FT-801 spectrometer in KBr pellets for
solids, or in thin films for liquid compounds. UV–vis spectra were taken in
dichloromethane solutions using a Hewlett Packard 8453 diode-array spectrometer,
while fluorescence spectra were recorded on Hitachi F-2500 fluorescence spectrometer.
The frontier molecular orbital (HOMO–LUMO) gaps of investigated compounds were
estimated from the onset of their –* absorption band. Fluorescence excitation spectra
were recorded to determine the excitation wavelength at which the maximum
fluorescence response is observed. Subsequent fluorescence emission spectra were
recorded at excitation wavelengths determined in this manner. The quantum yield of
examined compounds was determined relative to 9,10-diphenylanthracene – a known
quantum yield standard, using comparative method [1,2]. Using this method, the
quantum yield is calculated according to the following equation:
2
2
RR
Rn
n
m
m
where: Φ is the quantum yield, m is the slope of origin approaching linear segment of
the plot of integrated fluorescence intensity vs absorbance of a fluorophore solution, n is
the refractive index of solvent and subscript R refers to data for the solution of reference
fluorophore of known quantum yield – here: 9,10-diphenylanthracene in ethanol (ФR =
0.950 for excitation at 330–380 nm) and in cyclohexane (ФR = 0.955 for excitation at 366
nm) [3]. The 1H and 13C NMR spectra were obtained in CDCl3 with TMS as an internal
standard, using a Bruker DRX 400 spectrometer (400 and 100 MHz, respectively). The
13C NMR spectra were obtained in the J-modulation mode. The elemental analyses
were carried out on a Carlo Erba 1106 CHN analyzer. The melting points were
determined on a Kofler bench. The reaction course and purity of the products were
checked by thin-layer chromatography on Sorbfil UV-254 plates and were visualized
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with UV light. All chemicals were of analytical grade and purchased from Sigma-Aldrich
Chemical Co.
Experimental and analytical data
The synthesis of 1, 2, 3, 8, 10, 11, 15 is described in detail in Supporting Information of
reference [4].
2,5-Bis(3-decyl-2,2'-bithiophene-5-yl)-1,3,4-oxadiazole (13). A mixture of 11 (0.41 g,
0.6 mmol) and phosphorus oxychloride (7.58 g, 49.4 mmol) was refluxed for 5 h (the
completion of the reaction was monitored by TLC). The resulting solution was cooled to
room temperature, and poured on a mixture of crushed ice (10 g) in water (50 mL). It
was then neutralized by saturated solution of NaHCO3. The product was extracted with
CHCl3 (3 × 20 mL). The extract was washed with saturated aqueous sodium chloride
(30 mL), dried (Na2SO4) and concentrated. Then the solvent was evaporated under
reduced pressure. The crude product was purified by column chromatography using
benzene as eluent. Yield: 0.40 g (78%); yellow solid; Rf = 0.38 (silica gel, benzene or
CH2Cl2) mp 86–87 °С
IR (KBr). ν сm-1: 1580 (С=N).
1H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.88 (t, 3J=6.7 Hz, 6 H, 2СН3), 1.23-1.40
(m, 28H, 14СН2), 1.69 (m, 2Н, ThCH2CH2C8H17), 2.79 (t, 3J=7.8 Hz, 4H, 2Th-CH2),
7.10 (d.d, 3J=4.9 Hz, 3J=3.8 Hz, 2H, 2Th-4'-H), 7.23(d.d, 3J=3.5 Hz, 4J=0.5 Hz, 2H,
2Th-3'-H), 7.38 (d.d, 3J=5.1 Hz, 4J=0.6 Hz, 2H, 2Th-5'-H), 7.64(s, 2H, 2Th-4-H).
13C NMR (100 MHz, δ, ppm): 14.12 (СH3), 22.70, 29.27, 29.34, 29.43, 29.50, 29.58,
29.61, 30.47, 31.91 (СH2), 121.99 (2-Th), 126.64 (3′-Th), 127.03(5′-Th), 127.70(4′-Th),
132.36 (2-Th), 134.76 (5-Th), 135.94 (3-Th), 140.51 (2′-Th), 160.01 (2,5-Oxadiazole)
Elemental analysis. Calculated for С38H50N2S5: %C = 65.66, %H = 7.25, %N = 4.03;
found: %C = 65.56, %H = 7.28, %N = 4.13
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Ethyl 3-oxo-3-(2-thienyl)propanoate (4). Compound 4 was prepared according to the
known procedure [5] (see Supporting Information). Yield 87%. B.p. 164-168 °C (15-18
mmHg), lit. 143 °C (7 mmHg).
Ethyl 3-chloro-3-(2-thienyl)acrylate (5)
5.0 g (25 mmol) of freshly distilled compound 4 was slowly added with stirring to 11.5
mL (125 mmol) of phosphoryl chloride under cooling. Then 3.9 mL (28 mmol) of dry
triethylamine was added drop-wise during ca. 30 min. After the addition of 0.1 mL of
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) the reaction mixture was stirred for 30 min in
an ice bath, then for 6 h at 60–70 °C and finally left overnight at rt. The excess of POCl3
was removed under vacuum and the resulting mixture was treated with 100 g of
crushed ice. The product was extracted with dichloromethane (4 × 20 mL) and dried
over sodium sulfate. After removal of the solvent on a rotary evaporator, the final
residue was purified by column chromatography (SiO2/hexane-ethyl acetate 9:1)
yielding 4.1 g (76%) of yellow oil. Rf 0.35 (hexane-ethyl acetate 9:1).
IR (ν, cm-1): 1606 (C=C), 1721 (C=O), 2981 (C-Halk), 3106 (C-Har).
NMR 1Н (СDCl3, δ, ppm, J, Hz): 1.33 (3H, t, 3J= 7.1, ОСН2CH3); 4.26 (2H, q, 3J= 7.2,
ОСН2CH3); 6.53 (1H, s, C(Cl)=CH); 7.06 (1H, dd, 3J=5.0, 3J=3.8, Th-4-Н); 7.41 (1H, dd,
3J=5.1, 4J=1.0, Th-5-Н); 7.55 (1 H, dd, 3J=3.8, 4J=1.1, Th-3-Н);
NMR 13С (СDCl3, δ, ppm): 14.27 (ОСН2CH3), 60.57(ОСН2CH3), 113.39 (C(Cl)=CH),
128.09 (3(C)- Th), 129.16 (5(C)- Th),129.46 (4(C)- Th), 141.09 (2(C)- Th), 164.01
(С=O).
Elemental analysis. Calculated for C9H9ClO2S: %C = 49.89, %H = 4.19; found: %C =
48.56, %H = 4.28
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Ethyl 4-hydroxy-2,2'-bithiophene-5-carboxylate (6). 2.2 mL (20 mmol) of ethyl
thioglycolate was added to a solution of sodium ethylate, prepared from 0.92 g (40
mmol) of sodium and 75 mL of dry ethanol. The resulting mixture was stirred for an
additional 15 min under nitrogen. Then the solution of 4.0 g (18 mmol) of 5 in 5 mL of
dry ethanol was added dropwise to the resulting suspension and stirred for 1.5 h under
an inert atmosphere. The reaction mixture was concentrated in vacuum, dissolved in
150 mL of water, cooled and acidified with 2 М HCl to pH 3–4. The precipitate was
filtered out, then washed with water to pH 7. Recrystallization from methanol gave 2.2 g
(49%) of white powder. Mp 70–71 °C (methanol).
IR (ν, cm-1): 1097 (C-O-C), 1645 (C=O), 3083 [Wight] (O-H).
NMR 1Н (СDCl3, δ, ppm, J, Hz): 1.38 (3H, t, 3J= 7.1, ОСН2CH3); 4.36 (2H, q, 3J= 7.2,
ОСН2CH3); 6.28 (1H, s, Th-3-Н); 7.04 (1H, dd, 3J=5.1, 3J=3.7, Th-4’-Н); 7.28 (1H, dd,
3J=3.7, 4J=1.2, Th-5’-Н); 7.32 (1 H, dd, 3J=5.1, 4J=1.0, Th-3’-Н), 9.69 (1H, s, OH);
NMR 13С (СDCl3, δ, ppm): 14.37 (ОСН2CH3), 61.07(ОСН2CH3), 114.96 (3’(C)- Th),
125.40 (3(C)- Th), 126.63 (5’(C)- Th), 128.14 (4’(C)- Th), 136.48 (4(C)- Th),
142.32 (2’(C)- Th), 164.47 (С=O).
Elemental analysis. Calculated for C11H10O3S2: %C = 51.95, %H = 3.96; found: %C =
52.06, %H = 4.03
Ethyl 4-(hexyloxy)-2,2'-bithiophene-5-carboxylate (7). Potassium tert-butylate (0.86
g, 7.7 mmol) was added to a solution of 1.7 g (6.7 mmol) of 6 in 14 mL of dry DMSO
under nitrogen and the resulting mixture was stirred for 15 min. After the drop-wise
addition of 1.56 g (7.2 mmol) of 1-iodohexane to this mixture, it was stirred under inert
atmosphere for 4 h, then poured into 150 mL of ice water. The product was extracted
with dichloromethane (4 × 25 mL). The organic layer was washed with brine, dried over
MgSO4 and concentrated in vacuum. Purification by the column chromatography
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(SiO2/hexane-ethyl acetate 9:1) yielded 1.83 g (81%) of 7 as a green solid. Mp 40–
42 °C (hexane-ethyl acetate 9:1). Rf 0.39 (hexane-ethyl acetate 9:1).
IR (ν, cm-1): 1092 (C-O-C), 1700 (C=O); 2851, 2953 (C-Halk); 3098 (C-Har).
NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.92 (3H, t, 3J= 7.0, ОСН2CH3); 1.33-1.38 (7H, m,
(СН2)2, CH3) 1.50 (2H, m, CH2), 1.83 (2H, dd, 3J=14.9, 3J=6.9, CH2), 4.15 (2H, t, 3J=6.7,
OCH2), 4.31 (2H, q, 3J=7.0, ОСН2CH3); 6.90 (1H, s, Th-3-Н); 7.04 (1H, dd, 3J=5.1,
3J=3.5, Th-4’-Н); 7.27 (1H, dd, 3J=3.7, 4J=1.2, Th-5’-Н); 7.30 (1H, dd, 3J=5.1, 4J=1.2,
Th-3’-Н);
NMR 13С (СDCl3, δ, ppm): 14.00 (ОСН2CH3), 14.39 (CH3), 22.55, 25.47, 29.30, 31.50
((CH2)4), 60.42 (ОСН2CH3), 72.11 (ОСН2CH2), 112.94 (3(C)- Th), 124.97 (3’(C)- Th),
126.45 (5’(C)- Th), 128.12 (4’(C)- Th), 136.69 (2(C)- Th), 141.03 (2’(C)- Th),
161.09 (4(C)- Th), 161.70 (С=O).
Elemental analysis. Calculated for C17H22O3S2: %C = 60.32, %H = 6.55; found: %C =
60.38, %H = 6.61
4-(Hexyloxy)-2,2'-bithiophene-5-carboxylic acid (9). 1.0 g (3 mmol) of 7 dissolved in
5 mL of dry ethanol was added to a solution of 0.5 g (9 mmol) of potassium hydroxide in
8 mL of dry ethanol. The reaction mixture was heated to 50–60 °C and stirred for 4 h,
then cooled to rt and concentrated in vacuum. The residue was dissolved in 20 mL of
water and acidified with 2 M HCl to pH 3–4. The resulting suspension was vigorously
stirred for 20 min and filtered out. The precipitate was washed with ice water and dried.
Recrystallization from methanol gave 0.79 g (87%) of 9 as a white powder. Mp 134–136
°C (methanol).
IR (ν, cm-1): 1097 (C-O-C), 1649 (C=O), 2556 (C(=O)OH); 2857, 2947 (C-Halk); 3088
(C-Har).
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NMR 1Н ((СD3)2CO, δ, ppm, J, Hz): 0.83 (3H, t, 3J= 7.0, СН2CH3); 1.25-1.32 (4H, m,
(СН2)2) 1.45 (2H, m, CH2), 1.75 (2H, m, CH2), 2.68 (s, OH), 4.21 (2H, t, 3J=6.7,
OCH2); 7.06 (1H, dd, 3J=5.1, 3J=3.5, Th-4’-Н); 7.19 (1H, s, Th-3-Н); 7.38 (1H, dd,
3J=3.7, 4J=1.2, Th-5’-Н); 7.47 (1H, dd, 3J=5.1, 4J=1.2, Th-3’-Н);
NMR 13С ((СD3)2CO, δ, ppm): 12.26 (CH3), 21.24, 24.17, 28.13, 30.18 (4CH2), 71.00
(ОСН2CH2), 107.37 (5(C)- Th), 112.59 (3(C)- Th), 124.34 (3’(C)- Th), 125.71 (5’(C)- Th),
127.27 (4’(C)- Th), 135.27 (2(C)- Th), 139.92 (2’(C)- Th), 159.68 (4(C)- Th), 160.23
(С=O).
Elemental analysis. Calculeted for C15H18O3S2: %C = 58.04, %H = 5.84; found: %C =
58.08, %H = 5.91
N,N’-Bis[4-(hexyloxy)-2,2’-bithiophen-5-oyl]hydrazine (12). Oxalyl chloride (0.64 mL,
7.6 mmol) was added to a suspension of 9 (0.59 g, 1.9 mmol) in 6 mL of dry
dichloromethane under cooling (ice bath). After the addition of one drop of DMF to the
resulting mixture, it was stirred for 30 min under cooling then at rt for additional 2.5 h.
The solvent and the excess of oxalyl chloride were removed under reduced pressure
and the final product (acid chloride) was used in subsequent reactions without further
purification. Crude acid chloride was dissolved in 12 mL of dichloromethane, cooled in
an ice bath. Then, a mixture of 0.048 mL (0.95 mmol) of hydrazine hydrate and 0.92 mL
(11 mmol) of dry pyridine in 3 mL of dichloromethane was added dropwise. The reaction
mixture was stirred for 30 min under cooling and left overnight at rt. After removal of the
solvent in vacuum the residue was treated with 10 mL of ice water and stirred for 15
min. The precipitate was filtered out, washed with water and dried. Recrystallization
from methanol gave 0.35 g (60%) of 12 as a dark yellow solid. Mp 168–170 °C
(methanol). Rf 0.67 (chloroform).
IR (ν, cm-1): 1110 (C-O-C), 1608 (C=O); 2852, 2948 (C-Halk); 3080 (C-Har), 3348 (N-H).
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NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.91 (3H, m, СН2CH3); 1.38 (4H, m, (СН2)2) 1.53 (2H,
m, CH2), 1.97 (2H, m, CH2), 4.24 (2H, t, 3J=6.7, OCH2); 6.92 (1H, s, Th-3-Н); 7.05 (1H,
m, Th-4’-Н); 7.27 (1H, m, Thi-5’-Н); 7.29 (1H, m, Th-3’-Н), 10.13 (1H, s, NH);
NMR 13С (СDCl3, δ, m.d.): 14.02 (СН2CH3), 22.59, 25.41, 29.19, 31.39 ((CH2)4), 72.70
(ОСН2CH2), 111.91 (5(C)- Th), 112.01 (3(C)- Th), 125.01 (3’(C)- Th), 126.12 (4’(C)- Th),
128.21 (5’(C)- Th), 136.71 (2(C)- Th), 140.88 (2’(C)- Th), 156.50 (4(C)- Th), 156.75
(С=O).
Elemental analysis. Calculeted for C30H36N2O4S4: %C = 58.41, %H = 5.88, %N =
4.54; found: %C = 58.43, %H = 5.90, N = 4.60
2,5-Bis[4-(hexyloxy)-2,2’-bithiophen-5-yl]-1,3,4-oxadiazole (14). A mixture of 0.20 g
(0.32 mmol) of 12 and 3 mL of phosphoryl chloride was heated to 60–70 °C and stirred
for 6 h, then cooled to rt, poured in small portions into 100 g of crushed ice. The product
was extracted with chloroform (4 × 20 mL). The combined organic layers were washed
with 30 mL of ice water and the solvent was removed in vacuum. Chromatography
purification (SiO2/benzene-ethyl acetate 20:1) of the final residue gave 0.14 g (83%) of
14 as a bright yellow powder. Mp 104–106 °C (chloroform). Rf 0,53 (chloroform).
IR (ν, cm-1): 1113 (C-O-C); 1572, 1593 (C=N); 2852, 2926 (C-Halk); 3079, 3109 (C-Har).
NMR 1Н (СDCl3, δ, ppm, J, Hz): 0.89 (6H, m, СН2CH3); 1.33 (8H, m, (СН2)2) 1.55 (4H,
m, CH2), 1.89 (4H, m, CH2), 4.22 (4H, t, 3J=6.5, OCH2); 6.96 (2H, s, Th-4-Н); 7.05 (2H,
dd, 3J=5.1, 4J=3.5, Th-4’-Н); 7.27 (2H, dd, 3J=3.6, 4J=1.1, Thi-5’-Н); 7.30 (2H, dd,
3J=5.2, 4J=1.1, Th-3’-Н);
NMR 13С (СDCl3, δ, m.d.): 14.06 (СН2CH3), 22.63, 25.59, 29.47, 31.65 ((CH2)4), 72.38
(ОСН2CH2), 101.38 (2(C)- Th), 113.24 (4(C)- Th), 124.79 (3’(C)- Th), 125.96 (5’(C)- Th),
128.17 (4’(C)- Th), 136.57 (5(C)- Th), 139.28 (2’(C)- Th), 158.06 (С=N), 158.64(4(C)-
Th).
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Elemental analysis: Calculeted for C30H34N2O3S4: %C = 60.17, %H = 5.72, %N =
4.68; found: %C = 60.20, %H = 5.78, N = 4.70
3-Decyl-N-phenyl-2,2'-bithiophene-5-carboxamide (16). Oxalyl chloride (2.9 mL, 34
mmol) was added drop-wise into an anhydrous CH2Cl2 solution of 3-decyl-2,2'-
bithiophene-5-carboxylic acid (8, 1.99 g, 5.7 mmol) under vigorous stirring at 0 °С. The
reaction mixture was then additionally stirred at room temperature overnight. The
solvent and the excess of oxalyl chloride were evaporated under reduced pressure. The
resulting 3-decyl-2,2'-bithiophene-5-carboxylic acid chloride was used without
purification in the subsequent reaction. Aniline (5.7 mmol) was dissolved in dry ethyl
acetate (10 mL) in the presence of triethylamine (1.1 mL, 7.9 mmol). A solution of the
acid chloride (5.7 mmol) in 10 mL dry ethyl acetate was added drop-wise. A precipitate
was formed, and the mixture was stirred at room temperature overnight. Then, the
solvent was removed under reduced pressure. Water (7 mL) was added, and the solid
was collected on a filter, then washed three times with water. The resulting crude
product was purified by crystallization from methanol.
Yield: 2.06 g (82%); white solid; Rf = 0.59 (silica gel, hexane/EtOAc, 5/1) mp 88–90 °С
(methanol)
IR (ν, cm-1): 1631 (С=О), 3340 (N-H).
1H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.88 (t, 3J=6.8 Hz, 3 H, СН3), 1.25-1.35 (m,
14H, 7СН2), 1.62 (m, 2Н, ThCH2CH2C8H17), 2.72 (t, 3J=7.8 Hz, 4H, Th-CH2), 7.06-7.08
(d.d, 3J=5.1 Hz, 3J=3.6 Hz, 2H, 2Th-4'-H), 7.10-7.14 (m, 1H, Ph-4-H), 7.17 (d.d, 3J=3.6
Hz, 4J=1.2 Hz, 2H, 2Th-3'-H), 7.31-7.35 (m, 2H, Ph-3,5-H), 7.35 (d.d, 3J=5.2 Hz,
3J=3.6 Hz, H, Th-4'-H), 7.36(d.d, 3J=5.1 Hz, 4J=1.2 Hz, 2H, 2Th-5'-H), 7.49 (s, 1H, Th-4-
H), 7.61-7.63 (m, 2H, Ph-3,5), 7.88 (s, 1H, -NH-Ph).
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13C NMR (100 MHz, δ, ppm): 14.11 (СH3), 22.69, 29.33, 29.42, 29.48, 29.58, 29.61,
30.53, 31.91 (СH2), 120.30 (2,6-Ph), 124.55 (4-Ph), 126.51(3′-Th), 126.99 (4′-Th),
127.62 (5′-Th), 129.07 (3,5-Ph), 131.52 (4-Th), 135.05 (2-Th), 135.80 (3-Th), 136.29
(5-Th), 137,73 (2′-Th), 140.25 (1-Ph) 159.92 (-C(O)-NHPh).
Elemental analysis: Calculeted for C25H31NOS2: %C =70.54, %H =7.34, %N =3.29;
found: %C = 70.46, %H = 7.40, %N = 3.33
3,5-Bis(3-decyl-2,2'-bithiophen-5-yl)-4-phenyl-4H-1,2,4-triazole (18). PCl5 (0.23 g,
1.13 mmol) was added to a solution of 3-decyl-N-phenyl-2,2'-bithiophene-5-
carboxamide (16, 0.50 g, 1.13 mmol) in 3 mL of anhydrous benzene placed in an ice
bath. Then, the reaction mixture was stirred for 12 h at rt. After removing the solvent
under reduced pressure, the crude product was washed with dry methanol by
decantation. Residual amounts of methanol were removed on a vacuum evaporator. 3-
Decyl-N-phenyl-2,2'-bithiophene-5-carboximidoyl chloride (17) was used at once in the
subsequent reaction.
A mixture of 17 (1.13 mmol) and hydrazide 10 (0.41 g, 1.13 mmol) in anhydrous
N,N‐dimethylacetamide (5 mL) was heated at 165 °C for 6 h under nitrogen (the
completion of the reaction was monitored by TLC). The solvent was removed under
reduced pressure. 17 was purified by recrystallization from hexane or by column
chromatography using benzene/EtOAc (20/1) or CH2Cl2 as eluent.
Yield: 0.52g (62%); white solid; Rf = 0.29 (silica gel, /EtOAc, 20/1) mp 96–98 °С
IR (ν, cm-1) : 1497 (N=N)
1H NMR (400 MHz, CDCl3, δ, ppm, J, Hz): 0.89 (t, 3J=6.8 Hz, 6 H, 2СН3), 1.23-1.32
(m, 28H, 14СН2), 1.45 (m, 2Н, ThCH2CH2C8H17), 2.59(t, 3J=7.7 Hz, 4H, 2Th-CH2), 6.83
(s,2Th-4-H), 7.02 (d.d, 3J=5.1 Hz, 3J=3.5 Hz, 2H, 2Th-4'-H), 7.06 (d.d, 3J=3.5 Hz,
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4J=1.2 Hz, 2H, 2Th-3'-H), 7.29 (d.d, 3J=5.1 Hz, 4J=1.2 Hz, 2H, 2Th-5'-H), 7.45-7.48 (m,
2H, Ph-2,6-H), 7.61-7.71 (m, 3H, Ph-3,5,4-H).
13C NMR (100 MHz, δ, ppm): 14.12 (СH3), 22.70, 28.96, 29.27, 29.35, 29.40, 29.54,
29.62, 30.18, 31.93 (СH2), 125.39 (2-Th), 125.99 (2,6-Ph), 126.52 (4-Ph), 127.46
(3′-Th), 128.97 (5′-Th), 130.42 (4′-Th), 130.58 (3,5-Ph), 131.11 (4-Th), 133.58 (5-Th),
134.45 (3-Th), 135.09 (2′-Th), 139.61 (1,3,4-Triazole), 150.23 (1-Ph).
Elemental analysis: Calculated for C44H55N3S4: %C =70.07, %H =7.35, %N =5.57;
found: %C = 70.06, %H = 7.38, %N = 5.60
References
1. Williams, A. T. R.; Winfield, S. A.; Miller, J. N. Analyst, 1983, 108, 1067-1071.
2. Allen, M. W.; Measurement of Fluorescence Quantum Yields, Thermo Fisher
Scientific technical note 52019, Madison, WI, USA.
3. Brouwer, A. M. Pure and Applied Chemistry, 2011, 83, 2213-2228.
4. K. Kotwica, E. Kurach, G. Louarn, A. S. Kostyuchenko, A. S. Fisyuk, M. Zagorska, A.
Pron. Electrochimica Acta, 2013, 111, 491– 498
5. Y. Jiang; X. Chen; Y. Zheng; Z. Xue; C. Shu; W. Yuan; X. Zhang, Angew. Chem. Int.
Ed., 2011, 50, 7304–7307
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2,5-bis(3-decyl-2,2'-bithiophene-5-yl)-1,3,4-oxadiazole (BThOxDiaz) (13)
1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
Inte
nsity
18.72 3.462.292.021.020.97 0.95
Chloroform-d
TMS
M05
M00
M04
M01
M03
M02
7.6
47.3
97.3
87.2
37.2
27.1
1 7.1
07.0
9 2.8
12.7
92.7
7
1.7
21.7
11.6
91.6
71.6
5
1.3
91.3
21.2
61.2
3
0.8
90.8
80.8
6
S
S
S
S
O
NN
CH3
CH3
7.2 7.1
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
1.021.00
Chloroform-dM05
7.2
67.2
37.2
37.2
2
7.1
17.1
07.1
07.0
9
7.7 7.6 7.5 7.4
Chemical Shift (ppm)
0
0.1
0.2
Inte
nsity
0.97 0.95
7.6
4
7.3
97.3
97.3
8
13C NMR (100MHz)
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-1.0
-0.5
0
0.5
1.0
Inte
nsity
Chloroform-d
TMS
160.0
1 140.5
1140.2
8135.9
4134.7
6
132.3
6
127.7
0127.0
3126.6
4
121.9
9
77.3
677.0
476.7
2
31.9
1
29.6
129.5
829.3
422.7
0
14.1
2
0.0
0
S
S
SS
O
NN
CH3
CH3
S13
Ethyl 3-chloro-3-(2-thienyl)acrylate (5)
1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
Inte
nsity
3.332.231.081.05 0.98
Chloroform-d
TMS
7.5
57.5
47.4
27.4
2 7.4
17.2
6
7.0
77.0
67.0
5
6.5
3
4.2
84.2
64.2
54.2
3
1.3
51.3
31.3
1
0.0
0
S
Cl
O
OCH3
7.55 7.50 7.45 7.40
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
1.05 1.00
7.5
67.5
57.5
57.5
4
7.4
27.4
27.4
17.4
0
7.15 7.10 7.05 7.00 6.95
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
1.08
7.0
77.0
77.0
67.0
5
13C NMR (100MHz)
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-1.0
-0.5
0
0.5
Inte
nsity
Chloroform-d
TMS
164.0
1
141.0
9
129.4
6
128.0
8
113.3
9
77.3
777.0
576.7
4
60.5
7
14.2
7
0.0
0
S
Cl
O
O
CH3
S14
Ethyl 4-hydroxy-2,2'-bithiophene-5-carboxylate (6) 1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
Inte
nsity
3.412.261.091.060.78
Chloroform-d
TMS
9.6
9
7.3
2 7.3
17.2
87.2
87.2
6
7.0
5
6.8
2
4.3
94.3
74.3
54.3
4
1.4
01.3
81.3
6
0.0
0
S
S
OH
O
OCH3
7.30 7.25
Chemical Shift (ppm)
0
0.025
0.050
0.075
Inte
nsity
1.061.03
Chloroform-d
7.3
2 7.3
27.3
1 7.3
1
7.2
97.2
97.2
87.2
8
7.2
6
7.05 7.00
Chemical Shift (ppm)
0
0.025
0.050
0.075
Inte
nsity
1.097.0
57.0
47.0
47.0
3
13C NMR (100MHz)
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0
Chemical Shift (ppm)
-1.0
-0.9
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
Inte
nsity
Chloroform-d
TMS
164.4
7
142.3
2
136.4
8
128.1
4126.6
3125.4
0
114.9
6
77.3
677.0
376.7
2
61.0
7
14.3
7
0.0
0
S
S
OH
O
OCH3
S15
Ethyl 4-(hexyloxy)-2,2'-bithiophene-5-carboxylate (7).
1H NMR (400 MHz, CDCl3)
1H FAS704_001001R_FINAL.ESP
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
-0.02
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
Norm
alized Inte
nsity
3.007.012.002.002.002.020.981.041.001.01
CHLOROFORM-d
TMS
7.3
2 7.3
07.2
9
7.2
87.2
77.0
6
6.9
0
4.3
54.3
3 4.3
14.1
74.1
64.1
4
1.8
9
1.8
71.8
51.8
31.8
11.5
31.5
11.3
81.3
71.3
51.3
4
0.9
30.9
20.9
0
S
S
O
O
O
CH3
CH3
1H FAS704_001001R_FINAL.ESP
7.35 7.30 7.25 7.20 7.15
Chemical Shift (ppm)
0
0.025
0.050
Norm
alized Inte
nsity
1.001.01
7.3
27.3
27.3
1 7.3
07.2
9
7.2
87.2
87.2
7
1H FAS704_001001R_FINAL.ESP
7.05 7.00 6.95 6.90 6.85
Chemical Shift (ppm)
0
0.025
0.050
0.075
Norm
alized Inte
nsity
0.981.04
7.0
67.0
57.0
57.0
4
6.9
0
13C NMR (100MHz)
13C FAS704_001000FID_FINAL.ESP
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8
Chemical Shift (ppm)
-0.50
-0.45
-0.40
-0.35
-0.30
-0.25
-0.20
-0.15
-0.10
-0.05
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Norm
alized Inte
nsity
Chloroform-d
TMS
161.7
0161.0
9
141.0
3
136.6
9
128.1
2126.1
2124.9
7
112.9
4
108.2
5
72.1
1
60.4
2
31.5
0 29.3
0
25.4
7
22.5
5
14.3
914.0
0
S
S
O
CH3
O
O
CH3
S16
4-(Hexyloxy)-2,2'-bithiophene-5-carboxylic acid (9). 1H NMR (400 MHz, (CD3)2CO)
1H FAS846_001000FID.ESP
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
Norm
alize
d In
tensi
ty
3.374.082.042.052.000.980.980.980.94
Acetone-d6
TMS
7.4
77.4
6
7.3
8 7.3
87.1
9
7.0
67.0
67.0
5 4.2
34.2
14.1
9
2.7
0
1.7
91.7
7 1.7
51.7
31.4
91.4
7 1.4
51.4
11.3
01.2
91.2
91.2
8
0.8
50.8
30.8
1
S
S
O
O
OH
CH3
1H FAS846_001000FID.ESP
7.50 7.45 7.40 7.35
Chemical Shift (ppm)
0
0.1
0.2
Norm
alize
d In
tensi
ty
0.980.94
7.4
8 7.4
77.4
6 7.4
6
7.3
87.3
8 7.3
87.3
7
1H FAS846_001000FID.ESP
7.25 7.20 7.15 7.10 7.05 7.00
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
Norm
alize
d In
tensi
ty
0.980.98
7.1
9
7.0
77.0
67.0
67.0
5
13C NMR (100MHz)
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-0.05
0
0.05
Inte
nsity
Acetone-d6 Acetone-d6
TMS
204.1
6
160.2
3159.6
8
139.9
2
135.2
7
127.2
7124.3
4
112.5
9
107.3
7
71.0
0
30.1
828.1
324.1
721.2
4
12.2
6
0.0
0
S
S
O
OH
O
CH3
S17
N,N’-Bis[4-(hexyloxy)-2,2’-bithiophen-5-oyl]hydrazine (12)
1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Chemical Shift (ppm)
-0.02
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
Inte
nsity
3.90 1.631.031.03 1.030.49 0.43
Chloroform-d
TMS
10.1
3
7.3
1 7.2
97.2
87.2
77.0
67.0
56.9
2
4.2
64.2
44.2
3
2.0
01.9
91.9
71.9
51.9
3
1.5
51.5
31.3
81.3
71.2
51.2
20.9
30.9
10.9
0
0.0
0
S
S
O
NH
O
CH3
NH
O
S S
O
CH3
7.4 7.3 7.2 7.1 7.0 6.9
Chemical Shift (ppm)
0
0.05
0.10
0.15In
tensity
1.03 0.55 0.43
Chloroform-d
7.3
17.2
97.2
87.2
77.2
6
7.0
67.0
57.0
3
6.9
2
13C NMR (100MHz)
180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-0.5
0
0.5
Inte
nsity
Chloroform-d
TMS
156.7
5156.5
0
140.8
8
136.7
1
128.2
1
125.0
1
112.0
1
111.9
1
72.7
0
31.3
9 29.1
9
25.4
122.5
9
14.0
2
S S NH
O
O
CH3
NH
O
S
S
O
CH3
S18
2,5-Bis[4-(hexyloxy)-2,2’-bithien-5-yl]-1,3,4-oxadiazole (14)
1H NMR (400 MHz, CDCl3)
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
-0.02
-0.01
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
Inte
nsity
6.38 3.322.042.031.001.00 0.48
7.3
1
7.3
1 7.3
07.2
7
7.0
6
6.9
6
4.2
34.2
24.2
0
2.1
7
1.9
21.9
11.8
91.8
71.8
51.7
21.5
91.5
7 1.5
51.4
01.3
71.3
61.3
51.2
5
0.9
10.8
90.8
8
0.0
0
S
S
O
CH3
O
NN
S S
O
CH3
7.35 7.30 7.25
Chemical Shift (ppm)
0
0.025
0.050
Inte
nsity
1.000.94
7.3
1 7.3
17.3
0 7.3
0
7.2
8 7.2
77.2
67.2
6
7.10 7.05 7.00 6.95
Chemical Shift (ppm)
0
0.05
0.10
0.15
Inte
nsity
1.001.00
7.0
67.0
67.0
57.0
4
6.9
6
13C NMR (100MHz)
170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
Chemical Shift (ppm)
-0.5
0
0.5
1.0
Inte
nsity
Chloroform-d
TMS
158.6
4 158.0
6
139.2
8136.5
7
128.1
7124.7
9
113.2
4
101.3
8
77.3
677.0
476.7
372.3
8
31.6
5 29.4
7
25.5
922.6
3
14.0
6
0.0
0
S
S
O
CH3
O
NN
S S
O
CH3
S19
3-Decyl-N-phenyl-2,2'-bithiophene-5-carboxamide (16)
1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
Inte
nsity
14.09 3.042.031.991.92 1.751.000.84
Chloroform-d
TMS
M04
M06
M00
M03 M02
M01
7.8
87.6
37.6
27.6
17.4
97.3
57.3
37.3
17.1
87.1
87.0
87.0
7
2.7
42.7
22.7
0
1.6
91.6
3 1.6
2
1.5
81.3
11.2
9 1.2
71.2
5
0.8
90.8
80.8
6
S
S
CH3
NH
O
7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
1.92 1.75 1.07 1.000.990.970.84
Chloroform-d
M04M06
7.8
8
7.6
37.6
27.6
1
7.4
9
7.3
67.3
6 7.3
57.3
57.3
37.3
1
7.2
57.1
87.1
87.1
87.1
77.1
47.1
2
7.1
07.0
87.0
87.0
7
13C NMR (100MHz)
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-1.0
-0.5
0
0.5
Inte
nsity
Chloroform-d
TMS
159.9
2
140.2
5137.7
3136.2
9135.8
0135.0
5
131.5
2129.0
7127.6
2126.9
9120.3
0
77.3
677.0
476.7
3
31.9
1
29.6
129.3
3
22.6
9
14.1
1
0.0
0
S
S
CH3
O
NH
S20
3,5-Bis(3-decyl-2,2'-bithiophen-5-yl)-4-phenyl-4H-1,2,4-triazole (BThPhTriaz) (18)
1H NMR (400 MHz, CDCl3)
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
Inte
nsity
32.40 6.734.123.54 2.041.94
Chloroform-d
TMS
M04
M06
M07
M05
M08
M00
M03
M09
M02
M01
7.7
07.6
9
7.6
9 7.6
57.6
37.4
77.4
57.2
97.2
87.2
67.0
67.0
57.0
27.0
16.8
3
2.6
12.5
92.5
7
1.4
71.4
5
1.3
11.2
91.2
61.2
3
0.9
00.8
90.8
7
S
S
CH3
N
NNS
S
CH3
7.70 7.65 7.60 7.55 7.50 7.45 7.40
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
3.54 2.22
M08M09
7.7
07.6
97.6
97.6
7 7.6
7 7.6
5 7.6
37.6
2 7.6
17.6
1
7.4
87.4
77.4
6 7.4
57.4
5
7.25 7.20 7.15 7.10 7.05 7.00
Chemical Shift (ppm)
0
0.05
0.10
Inte
nsity
2.02 2.001.94
Chloroform-d
M06M07
M05
7.3
07.2
97.2
87.2
87.2
6
7.0
67.0
67.0
57.0
57.0
3
7.0
27.0
1
13C NMR (100MHz)
200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
-1.0
-0.5
0
0.5
1.0
Inte
nsi
ty
Chloroform-d
TMS
150
.23
139
.61
135
.09
133
.58
131
.11
130
.58
130
.42
128
.97
127
.46
126
.52
125
.99
125
.77
125
.39
125
.29
77.
3877.
0676.
74 31.
93 29.
6229.
3528.
9622.
70
14.12
0.0
0
S
S
CH3
N
NN
S
S
CH3