D. Lumpi et al. / Tetrahedron Letters 50 (2009) 6469–6471
6471
Table 2
5. (a) Yamamoto, Y.; Yoshioka, H.; Takehana, T.; Yoshimura, S.; Kubo, K.;
Nakamoto, K. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 2009, 50, 161–
162; (b) Guiotto, A.; Canevari, M.; Pozzobon, M.; Moro, S.; Orsolini, P.;
Veronese, F. M. Bioorg. Med. Chem. 2004, 12, 5031–5037; (c) Lee, L. S.; Conover,
C.; Shi, C.; Whitlow, M.; Filpula, D. Bioconjugate Chem. 1999, 10, 973–
981.
6. Braunshier, C.; Hametner, C.; Froehlich, J.; Schnoeller, J.; Hutter, H. Tetrahedron
Lett. 2008, 49, 7103–7105.
7. Braunshier, C.; Hametner, C. QSAR Comb. Sci. 2007, 26, 908–918.
8. Keegstra, E. M. D.; Zwikker, J. W.; Roest, M. R.; Jenneskens, L. W. J. Org. Chem.
1992, 57, 6678–6680.
Yields for the preparation of 4a–d
Entry
Tritylate 3
Product 4
Yielda (g)
Yielda (%)
1
2
3
4
3a
3b
3c
3d
4a
4b
4c
4d
5.5
53.2
9.0
98
96
98
99
10.8
a
Isolated yields; reaction conditions: 80% AcOH, 40 °C, 2 h.
9. (a) Heise, H. M.; Kuepper, L.; Butvina, L. N. Anal. Bioanal. Chem. 2003, 375, 1116–
1123; (b) Bentrup, U.; Kuepper, L.; Budde, U.; Lovis, K.; Jaehnisch, K. Chem. Eng.
Technol. 2006, 29, 1216–1220; (c) Minnich, C. B.; Buskens, P.; Steffens, H. C.;
Baeuerlein, P. S.; Butvina, L. N.; Kuepper, L.; Leitner, W.; Liauw, M. A.; Greiner, L.
Org. Process Res. Dev. 2007, 11, 94–97.
10. Jaumot, J.; Gargallo, R.; de Juan, A.; Tauler, R. Chemometr. Intell. Lab. Syst. 2005,
76, 101–110.
11. Synthesis of 1,1,1,27,27,27-hexaphenyl-2,5,8,11,14,17, 20,23,26-nonaoxahep-
under inert conditions. The scope of possible applications is
widespread. In the field of organic chemistry one can imagine to
apply this technique to, for example, metalation reactions, depro-
tonations, catalytic reactions under inert atmosphere (transition
metal assisted coupling, olefin metathesis), etc. Experimental work
covering some of these projects is already in progress. Further-
more, the possibility of elucidation of reaction mechanisms by
monitoring transition states is clearly visible. This field of applica-
tion is more sophisticated and will therefore be the aim of future
projects.
tacosane 3b. Under argon,
a 4-neck round bottom flask equipped with
mechanical stirrer, reflux condenser, thermometer (and dropping funnel,
respectively) and the ATR-IR Probe inlet was charged with sodium hydride
(12.00 g, 500 mmol, 2.5 equiv) and dry THF (500 mL). To the well stirred
suspension was added a solution of mono-trityl protected glycol 1a (139.38 g,
400 mmol, 2.0 equiv) in dry THF (500 mL) at room temperature. After
completion of the reaction according to IR-monitoring (4 h), the mixture was
cooled to 0 °C and a solution of di-tosylated glycol 2b (100.52 g, 200 mmol,
1.0 equiv) in dry THF (500 mL) was added. The temperature was adjusted to
40 °C and the suspension was stirred for 80 h. For workup, the reaction mixture
was poured onto ice water (1200 mL)/chloroform (800 mL). The phases were
separated and the aqueous phase was extracted with chloroform (500 mL). The
combined organic layers were washed with brine (500 mL) and dried over
sodium sulfate. After removing the solvent under reduced pressure, the title
compound was obtained as a clear, slightly orange, viscous oil. Yield: 165.36 g
(97%). 1H NMR (200 MHz, DMSO-d6) d = 7.48–7.15 (m, 30 H), 3.67–3.39 (m, 28
H), 3.06 (t, J = 4.8 Hz, 4 H); 13C APT NMR (50 MHz, DMSO-d6) d = 143.8 (s),
128.2 (d), 127.8 (d), 126.9 (d), 85.9 (t), 70.1 (t), 69.9 (t), 69.85 (t), 69.82 (t),
69.77 (t), 69.7 (t), 63.0 (t). Anal. Calcd for C54H62O9 (855.09): C, 75.85; H, 7.31.
Found: C, 76.15; H, 7.15; N, <0.05.
Acknowledgements
The authors want to thank A.R.T. Photonics for providing us
with the mid-IR fibre optic probes used in this work. The financial
support granted by the Austrian Science Fund within the project
L416-N17 is also acknowledged.
Supplementary data
12. Synthesis of 3,6,9,12,15,18,21-heptaoxatricosane-1,23-diol 4b. Compound 3b
(128.26 g, 150 mmol) was stirred with 80% acetic acid (1200 mL) at 40 °C. After
2 h the reaction was completed according to HPLC analysis. The mixture was
allowed to cool to room temperature and poured onto ice water (600 mL). The
Supplementary data (experimental details and compound char-
acterization data of substances 3a–d and 4a–d, copies of spectra
(1H NMR, 13C NMR, IR)) associated with this article can be found,
precipitate was filtered off over
a glass sinter funnel. The filtrate was
concentrated under reduced pressure leaving a cloudy oil. The crude product
was mixed with cold water (500 mL) and the suspension was again filtered
over the same glass sinter funnel, still containing the bed of triphenylmethanol
formed during the first filtration. The filter cake was washed with cold water,
giving 77.02 g (99%) of pure triphenylmethanol after drying at 40 °C/15 mbar.
The solvent of the filtrate was removed under reduced pressure (0.05 mbar) to
afford the title compound as a clear, slightly orange oil. Yield: 53.20 g (96%). 1H
NMR (200 MHz, CDCl3) d = 3.62–3.38 (m, 32 H), 3.30 (br s, 2 H). 13C NMR
(50 MHz, CDCl3) d = 72.2, 70.15, 70.10, 69.9, 61.1. Anal. Calcd for C16H34O9
(370.44): C, 51.88; H, 9.25. Found: C, 51.81; H, 9.34; N, <0.05.
References and notes
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3 d results in almost a quantitative formation of the
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