Electronic Supporting Information
One-pot synthesis of p-tert-butylthiacalix[6/8]arenes
Takashi Kimuroa, Manabu Yamadab*, Fumio Hamadaa*
a
Department of Applied Chemistry for Environments, Graduate School of Engineering and Resource
Science, Akita University, 1-1
Tegatagakuen-machi, Akita 010-8502, Japan
b
Research Center for Engineering Science, Graduate School of Engineering Resource Science, Akita
University, 1-1 Tegatagakuen-machi, Akita 010-8502, Japan
*
Corresponding Author (M. Y.): myamada@gipc.akita-u.ac.jp; Tel.: +81-18-889-3068; Fax: +81-18-889-3068.
*
Corresponding Author (F. H.): hamada@gipc.akita-u.ac.jp; Tel.: +81-18-889-2440; Fax: +81-18-889-2440.
1
Supporting Information Comprises:
Experimental Section
Materials and instrumentations
Synthetic procedure and physical property of p-tert-butylthiacalix[n]arenes
Supporting figures and table
Supplementary Figure S1 1H NMR spectrum of run 1.
Supplementary Figure S2 1H NMR spectrum of 1 after isolation.
Supplementary Figure S3 1H NMR spectrum of 2 after isolation.
Supplementary Figure S4 1H NMR spectrum of run 2.
Supplementary Figure S5 1H NMR spectrum of run 3.
Supplementary Figure S6 1H NMR spectrum of run 4.
Supplementary Figure S7 MS spectra of 2 decomposition experimental at 2 h (left) and 24 h (right).
Supplementary Figure S8 1H NMR spectrum of 2 decomposition experimental.
Supplementary Figure S9 MS spectra of 3 decomposition experimental at 2 h (left) and 24 h (right).
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Experimental Section
Materials and instrumentations
All solvents were purchased from commercial sources, and used as received. The reactions were carried out
in nitrogen atmosphere. 1H NMR spectra were taken on Bruker DPX 300 spectrometer. Chemical shifts are
quoted as parts per million (ppm) relative to tetramethylsilane (CDCl3). MALDI-TOF MS spectra were
taken on Bruker autoflexspeed-AK1.
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Synthetic procedure and physical property of p-tert-butylthiacalix[n]arenes
1) S8 , NaOH , 180 oC , 24 h
2) S8 ,NaOH , 230 oC , several hours
Ph2O , N2
OH
S
OH
n (n = 4,6,8)
Under nitrogen atmosphere, p-tert-butylphenol (30.0 g, 0.200 mol) was dissolved in diphenyl ether (Ph2O,
50 mL) at 100°C. Sulfur (10.7 g, 0.333 mol) and NaOH (0.160 g, 4.00 mmol) were added, and the mixture
was heated at 130°C for 2 h, followed by 180°C for 24 h. After cooling to 100°C, additional sulfur (5.00 g,
0.156 mol) and NaOH (3.99 g, 0.100 mol) were introduced and heating was resumed at 230°C for 5‒24 h.
After cooling to room temperature, chloroform (100 mL) and 2N H2SO4 (100 mL) were added. The organic
layer was washed with saturated aqueous Na2SO4 and water, and concentrated in vacuo to give a viscous
material. After the removal of Ph2O by distillation under reduced pressure, precipitates were obtained upon
the addition of acetone. The solids, consisting of 1, 2, and 3, were filtered. The compounds were separated
by fractional crystallization from a small amount of chloroform. Pure octamer 3 was isolated first as a white
powder, and the hexamer 2 was next recovered. Finally, the tetramer 1 crystallized from the mother liquor.
1
H NMR (300 MHz, CDCl3, TMS) 1: δ 9.60 (s, 4H; Ar-OH), 7.61 (s, 8H; Ar-H), 1.22 (s, 36H, tert-butyl); 2:
δ 9.20 (s, 6H; Ar-OH), 7.57 (s, 12H; Ar-H), 1.22 (s, 54H, tert-butyl); 3: δ 8.70 (s, 8H; Ar-OH), 7.54 (s, 16H;
Ar-H), 1.22 (s, 72H, tert-butyl).
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Supporting figures and table
Supplementary Figure S1 1H NMR spectrum of run 1. A peak of 9.6 ppm attributed to hydroxyl groups of
1 and 9.2 ppm attributed to hydroxyl groups of 2. The peaks of 7.63 ppm and 7.59 ppm attributed to Ar-H of
1 and 2, respectively. A peak of 1.2 ppm attributed to all tert-Butyl groups of 1 and 2.
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Ar-OH (1)
t-butyl
CHCl3
TMS
Ar-H
Ar-OH
H2O
Supplementary Figure S2 1H NMR spectrum of 1 after isolation. A peak of 9.6 ppm attributed to hydroxyl
groups of 1. The peaks of 7.63 ppm attributed to Ar-H of 1. A peak of 1.2 ppm attributed to tert-Butyl groups
of 1.
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Ar-OH (2)
t-butyl
CHCl3
Ar-H
TMS
Ar-OH
H2O
Supplementary Figure S3 1H NMR spectrum of 2 after isolation. A peak of 9.2 ppm attributed to hydroxyl
groups of 2. The peaks of 7.59 ppm attributed to Ar-H of 2. A peak of 1.2 ppm attributed to tert-Butyl groups
of 2.
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Supplementary Figure S4 1H NMR spectrum of run 2. A peak of 9.6 ppm attributed to hydroxyl group of 1.
9.2 ppm and 8.7 ppm attributed to hydroxyl group of 2 and 3, respectively. The peaks of around 7.6 ppm
attributed to Ar-H of 1, 2, and 3, respectively. A peak of 1.2 ppm attributed to tert-Butyl groups of 1, 2, and
3.
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Supplementary Figure S5 1H NMR spectrum of run 3. A peak of 9.6 ppm attributed to hydroxyl group of 1
and 8.7 ppm attributed to hydroxyl group of 3. The peaks of 7.63 ppm and 7.57 ppm attributed to Ar-H of 1
and 3, respectively. A peak of 1.2 ppm attributed to tert-Butyl groups of 1 and 3.
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Supplementary Figure S6 1H NMR spectrum of run 4. A peak of about 9.6 ppm attributed to hydroxyl
group of 1 and about 8.7 ppm attributed to hydroxyl group of 3. The peaks of 7.63 ppm and 7.56 ppm
attributed to Ar-H of 1 and 3, respectively. A peak of 1.2 ppm attributed to tert-Butyl groups of 1 and 3.
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Supplementary Figure S7 MS spectra of 2 decomposition experimental at 2 h (left) and 24 h (right).
The structures of tetrameric, pentameric, and hexameric estimated a, b, and c, respectively (X is S- or SH).
S
OH
S
and
X
OH
2 OH
S
OH
4
a
1
S
OH
S
OH
X
3
OH
b2
S
OH
S
OH
X
4 OH
and
S
OH
6
c3
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Supplementary Figure S8 1H NMR spectrum of 2 decomposition experimental. A peak of 9.6 ppm
attributed to hydroxyl group of 1. A peak of 7.63 ppm attributed to Ar-H of 1. A peak of 1.2 ppm attributed
to tert-Butyl group of 1.
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Supplementary Figure S9 MS spectra of 3 decomposition experimental at 2 h (left) and 24 h (right). It is
expected that the following compounds exist in the sample (X is S- or SH).
S
OH
S
OH
X
OH
2~8
and
S
OH
4, 6, 8
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