Electronic Supporting Information

One-pot synthesis of p-tert-butylthiacalix[6/8]arenes

Takashi Kimuroa, Manabu Yamadab*, Fumio Hamadaa*

aDepartment of Applied Chemistry for Environments, Graduate School of Engineering and Resource Science, Akita University, 1-1

Tegatagakuen-machi, Akita 010-8502, Japan

bResearch Center for Engineering Science, Graduate School of Engineering Resource Science, Akita University, 1-1 Tegatagakuen-machi, Akita 010-8502, Japan

*Corresponding Author (M. Y.): ; Tel.: +81-18-889-3068; Fax: +81-18-889-3068.

*Corresponding Author (F. H.): ; Tel.: +81-18-889-2440; Fax: +81-18-889-2440.

Supporting Information Comprises:

Experimental Section

Materials and instrumentations

Synthetic procedure and physical property ofp-tert-butylthiacalix[n]arenes

Supporting figures and table

Supplementary Figure S1 1H NMR spectrum of run1.

Supplementary Figure S2 1H NMR spectrum of1after isolation.

Supplementary Figure S3 1H NMR spectrum of 2after isolation.

Supplementary Figure S41H NMR spectrum of run2.

Supplementary Figure S51H NMR spectrum of run3.

Supplementary Figure S61H NMR spectrum of run4.

Supplementary Figure S7MS spectra of 2 decomposition experimental at 2 h (left) and 24 h (right).

Supplementary Figure S81H NMR spectrum of2 decomposition experimental.

Supplementary Figure S9MS spectra of 3 decomposition experimental at 2 h (left) and 24 h (right).

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 onBruker DPX 300 spectrometer.Chemical shifts are quoted as parts per million (ppm) relative to tetramethylsilane (CDCl3). MALDI-TOF MS spectra weretaken on Bruker autoflexspeed-AK1.

Synthetic procedure and physical property of p-tert-butylthiacalix[n]arenes

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.

1H NMR (300 MHz, CDCl3, TMS) 1: δ9.60 (s, 4H; Ar-OH), 7.61 (s, 8H; Ar-H), 1.22 (s, 36H, tert-butyl); 2:δ9.20 (s, 6H; Ar-OH),7.57 (s, 12H; Ar-H),1.22 (s, 54H, tert-butyl); 3: δ8.70 (s, 8H; Ar-OH), 7.54 (s, 16H; Ar-H),1.22 (s, 72H, tert-butyl).

Supporting figures and table

Supplementary Figure S1 1H NMR spectrum of run1. 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.

Supplementary Figure S21H NMR spectrum of 1after 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.

Supplementary Figure S31H NMR spectrum of 2after 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.

Supplementary Figure S41H 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.

Supplementary Figure S51H 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.

Supplementary Figure S61H 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.


Supplementary Figure S7MS 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).


Supplementary Figure S81H NMR spectrum of2 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.

Supplementary Figure S9MS 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).

1