PAPER
Preparation of para-Terphenylylalkanethiols
1003
4-[1.1¢;4¢.1¢¢]Terphenyl-4-ylbutan-1-ol (15a)
1H NMR (200 MHz, CDCl3/TMS): d = 1.23 (s, 9 H, CH3), 1.24–
1.65 (series of m, 8 H, H-2chain, H-3chain, H-4chain, H-5chain), 2.65 (t,
J = 7.6 Hz, 2 H, H-6chain), 2.83 (t, J = 7.2 Hz, 2 H, H-1chain), 7.24–
7.63 (m, 9 H, CHarom-H-2, H-3, H-5, H-6, H-2¢¢ to H-6¢¢), 7.66 (s,
4 H, CHarom-H-2¢, H-3¢, H-5¢, H-6¢).
13C{1H} NMR (50 MHz, CDCl3/TMS): d = 27.4 (CH3), 28.5
(C-3chain), 28.7 (C-4chain), 28.8 (C-2chain), 29.5 (C-5chain), 31.3
(C-1chain), 35.5 (C-6chain), 46.4 [C(CH3)3], 126.8, 126.9, 127.2,
127.4, 128.7, 128.8 (C-2, C-3, C-5, C-6, C-2¢, C-3¢, C-5¢, C-6¢, C-2¢¢
to C-6¢¢), 137.9, 139.7, 140.0, 140.7, 141.9 (C-1, C-4, C-1¢, C-4¢, C-
1¢¢), 206.9 (C=O).
Yield: 2.0 g (90%); pale orange solid.
1H NMR (200 MHz, CDCl3/TMS): d = 1.62–1.78 (series of m, 4 H,
H-2chain, H-3chain), 2.71 (t, J = 7.2 Hz, 2 H, H-4chain), 3.70 (t,
J = 6.2 Hz, 2 H, H-1chain), 7.30–7.64 (m, 9 H, CHarom-H-2, H-3, H-
5, H-6, H-2¢¢ to H-6¢¢), 7.67 (s, 4 H, CHarom-H-2¢, H-3¢, H-5¢, H-6¢).
6-[1.1¢;4¢.1¢¢]Terphenyl-4-ylhexan-1-ol (15c)
Yield: 1.3 g (82%); white solid; mp 180 °C.
1H NMR (200 MHz, CDCl3/TMS): d = 1.25–1.59 (series of m, 8 H,
H-2chain to H-5chain), 2.67 (t, J = 7.8 Hz, 2 H, H-6chain), 3.66 (t,
J = 6.3 Hz, 2 H, H-1chain), 7.25–7.63 (m, 9 H, CHarom-H-2, H-3, H-
5, H-6, H-2¢¢ to H-6¢¢), 7.67 (s, 4 H, CHarom-H-2¢, H-3¢, H-5¢, H-6¢).
Thiopivalic Acid S-(11-[1.1¢;4¢.1¢¢]terphenyl-4-yl-undecyl) Ester
(16d)
Yield: 0.20 g (53%); white solid; mp 123–124 °C.
11-[1,1¢;4¢,1¢¢]Terphenyl-4-ylundecan-1-ol (15d)
Yield: 0.30 g (77%); white wax.
1H NMR (400 MHz, CDCl3/TMS): d = 1.20 (s, 9 H, CH3), 1.25–
1.90 (series of m, 18 H, H-2chain to H-10chain), 2.66 (t, J = 7.8 Hz,
2 H, H-11chain), 2.83 (t, J = 7.4 Hz, 2 H, H-1chain), 7.20–7.66 (m,
9 H, CHarom-H-2, H-3, H-5, H-6, H-2¢¢ to H-6¢¢), 7.68 (s, 4 H,
CHarom-H-2¢, H-3¢, H-5¢, H-6¢).
1H NMR (400 MHz, CDCl3/TMS): d = 1.20–1.73 (series of m,
18 H, H-2chain to H-10chain), 2.67 (t, J = 7.8 Hz, 2 H, H-11chain), 3.67
(t, J = 6.3 Hz, 2 H, H-1chain), 7.20–7.65 (m, 9 H, CHarom-H-2, H-3,
H-5, H-6, H-2¢¢ to H-6¢¢), 7.67 (s, 4 H, CHarom-H-2¢, H-3¢, H-5¢, H-
6¢).
Reductive Cleavage of Thio Esters 6, 16a–d; 5-[1.1¢;4¢.1¢¢]Ter-
phenyl-4-ylpentan-1-thiol (17b); Typical Procedure
Thio-Mitsunobu Reaction; Thiopivalic Acid S-(5-[1.1¢;4¢.1¢¢]ter-
phenyl-4-ylpentyl) Ester (16b); Typical Procedure
To a suspension of LiAlH4 (0.34 g, 9.0 mmol) in THF (5 mL) was
added slowly a solution of thioester 15b (1.2 g, 2.9 mmol) in THF
(50 mL). After 1 h, the mixture was hydrolyzed with 1 M HCl
(20 mL) and extracted with CH2Cl2 (3 × 75 mL). After the removal
of the solvent, the crude product was filtered over silica gel (hex-
ane–CH2Cl2, 1:1). Evaporation of the solvent afforded a white solid;
yield: 0.88 g (90%). For analytical data, see Table 1.
A solution of Ph3P (2.9 g, 11 mmol) in THF (30 mL) was cooled to
0 °C. Diisopropyl azodicarboxylate (2.3 mL, 12 mmol) was added
dropwise and a yellow precipitate was formed. To the cooled mix-
ture, a suspension of 15b (1.8 g, 11 mmol) and thiopivalic acid (5;
1.3 mL, 11 mmol) in THF (60 mL) was added slowly. The cooling
was removed and the mixture was stirred for 1 h. After refluxing for
2 h, the solvent was removed. The residue was mixed with EtOH,
which was afterwards removed in vacuo. The residue was subjected
to flash chromatography (silica gel, hexane–CH2Cl2, 4:1 → 2:1) to
give a crude product, which was crystallized from EtOH giving a
white solid; yield: 1.2 g (26%); mp 149 °C.
References
(1) Flink, S.; van Veggel, F. C. J. M.; Reinhoudt, D. N. Adv.
Mater. 2000, 12, 1315.
(2) Dudek, S. P.; Sikes, H. D.; Chidsey, C. E. D. J. Am. Chem.
Soc. 2001, 123, 8033.
(3) Lahiri, J.; Ostuni, E.; Whitesides, G. M. Langmuir 1999, 15,
2055.
(4) Pirrung, M. C. Angew. Chem. Int. Ed. 2002, 41, 1276.
(5) Xia, Y.; Whitesides, G. M. Angew. Chem. Int. Ed. 1998, 37,
550.
(6) Murgin, T.; Choong, V.; Maracas, G. Langmuir 2000, 16,
5371.
(7) Xia, Y.; Whitesides, G. M. Ann. Rev. Mater. Sci. 1998, 28,
153.
(8) Slomon, A.; Cahen, D.; Lindsay, S.; Tomfohr, J.; Engelkes,
V. B.; Frisbie, C. D. Adv. Mater. 2003, 15, 1881.
(9) Wang, W.; Lee, T.; Reed, M. A. Phys. Rev. B 2003, 68,
35416.
(10) Himmel, H. J.; Terfort, A.; Wöll, C. J. Am. Chem. Soc. 1998,
120, 12069.
(11) Cologne, J.; Buendia, J.; Sabadie, J. Bull. Soc. Chim. Fr.
1967, 83, 4370.
1H NMR (200 MHz, CDCl3/TMS): d = 1.23 (s, 9 H, CH3), 1.47–
1.69 (series of m, 6 H, H-2chain, H-3chain, H-4chain), 2.66 (t,
J = 7.6 Hz, 2 H, H-5chain), 2.84 (t, J = 7.2 Hz, 2 H, H-1chain), 7.24–
7.63 (m, 9 H, CHarom-H-2, H-3, H-5, H-6, H-2¢¢ to H-6¢¢), 7.66 (s,
4 H, CHarom-H-2¢, H-3¢, H-5¢, H-6¢).
13C{1H} NMR (50 MHz, CDCl3/TMS): d = 27.4 (CH3), 28.4
(C-3chain), 28.5 (C-2chain), 29.4 (C-4chain), 30.9 (C-1chain), 35.4
(C-5chain), 46.4 [C(CH3)3], 126.8, 126.9, 127.2, 127.4, 128.7, 128.8
(C-2, C-3, C-5, C-6, C-2¢, C-3¢, C-5¢, C-6¢, C-2¢¢ to C-6¢¢), 138.0,
139.7, 139.9, 140.6, 141.7 (C-1, C-4, C-1¢, C-4¢, C-1¢¢), 206.9
(C=O).
Thiopivalic Acid S-(4-[1.1¢;4¢.1¢¢]terphenyl-4-ylbutyl) Ester
(16a)
Yield: 1.5 g (56%); white solid; mp 156 °C.
1H NMR (200 MHz, CDCl3/TMS): d = 1.23 (s, 9 H, CH3), 1.63–
1.75 (series of m, 4 H, H-2chain, H-3chain), 2.68 (t, J = 7.3 Hz, 2 H,
H-4chain), 2.88 (t, J = 7.0 Hz, 2 H, H-1chain), 7.24–7.63 (m, 9 H,
CHarom-H-2, H-3, H-5, H-6, H-2¢¢ to H-6¢¢), 7.66 (s, 4 H, CHarom-H-
2¢, H-3¢, H-5¢, H-6¢).
13C{1H} NMR (50 MHz, CDCl3/TMS): d = 27.4 (CH3), 28.3
(C-2chain), 29.2 (C-3chain), 30.6 (C-1chain), 35.0 (C-4chain), 46.4
[C(CH3)3], 126.9, 127.0, 127.3, 127.5, 128.8, 128.9 (C-2, C-3, C-5,
C-6, C-2¢, C-3¢, C-5¢, C-6¢, C-2¢¢ to C-6¢¢), 138.2, 139.9, 140.0,
140.7, 141.4 (C-1, C-4, C-1¢, C-4¢, C-1¢¢), 207.0 (C=O).
(12) Drefahl, G.; Tahlmann, K. J. Prakt. Chem. 1963, 20, 56.
(13) Quelet, R. Bull. Soc. Chim. Fr. 1929, 45, 75.
(14) During this work, the synthesis of 11 using a somewhat
different route was published: Ishida, T.; Mizutani, W.;
Choi, N.; Akiba, U.; Fujihira, M.; Tokumoto, H. J. Phys.
Chem. B 2000, 104, 1680.
(15) Belmar, J.; Téllez, J.; Baeza, J.; Freer, J. Z. Naturforsch., B:
Chem. Sci. 2000, 55, 583.
(16) Volante, R. P. Tetrahedron Lett. 1981, 22, 3119.
(17) Mitsunobu, O. Synthesis 1981, 1.
(18) Kulkarni, S. U.; Patil, V. D. Heterocycles 1982, 18, 163.
Thiopivalic Acid S-(6-[1.1¢;4¢.1¢¢]terphenyl-4-ylhexyl) Ester
(16c)
Yield: 1.0 g (60%); white solid; mp 144 °C.
Synthesis 2005, No. 6, 998–1004 © Thieme Stuttgart · New York