S.Chatti et al./ Tetrahedron 57 ꢀ2001) 4365±4370
4369
7
ꢀ
.1.1. Tosylation of n-octanol. p-Toluenesulfonyl chloride
23 g, 120 mmol) was added over a period of 30 min to a
Acknowledgements
stirred solution of pyridine ꢀ31.6 g, 400 mmol) and
n-octanol ꢀ13 g, 100 mmol) maintained at 08C. The reaction
mixture was allowed to stirr for 3 additional hours and then
quenched with H O ꢀ200 mL) and extracted with CH Cl
2
We are grateful to the Soci e t e Roquette-Fr eÁ res ꢀLestrem,
France) for a kind gift of dianhydrohexitols and to the
Higher Education Ministry of Tunisia for ®nancial support.
2
2
ꢀ
3£60 mL), and the combined organic layers were washed
with 3 M HCl ꢀ3£80 mL) followed by 10% NaHCO
3
ꢀ
1£80 mL). The organic layer was dried over Na SO and
References
2
4
concentrated under vacuum and the crude product puri®ed
by silica gel chromatography.
1. Fl eÁ che, G.; Huchette, M. Starch/St aÈ rke 1986, 38, 26.
2
. Jacquet, F.; Gaset, A.; Gorrichon, J. P. Inform.Chim. 1984, 30,
1431.
2
n-octyl 4-p-toluenesulphonate: colourless oil. H NMR
1
1
ꢀ
ꢀ
2
200 MHz, CDCl ): d 0.90 ꢀt, 3H, J7.2 Hz), 1.08±1.82
3. Kricheldorf, H. R. Rev.Macromol.Chem.Phys. 1997, 37, 599.
4. Stross, P.; Hemmer, R. Adv.Carbohydr.Chem.Biochem.
1991, 49, 93.
3
m, 12 H), 2.44 ꢀs, 3H), 4.03 ꢀt, 2H, J6.9 Hz), 7.36 ꢀd,
H, J8.3 Hz), 7.90 ꢀd, 2H, J8.3 Hz).
5
. Chatti, S.; Bortolussi, M.; Loupy, A. Tetrahedron Lett. 2000,
41, 3367.
7.1.2. Mesylation of n-octanol. A stirred solution of
CH Cl2 ꢀ240 mL), n-octanol ꢀ10.53 g, 81 mmol), and
2
6. Chatti, S.; Bortolussi, M.; Loupy, A. Tetrahedron 2000, 56,
5877.
triethylamine ꢀ12.33 g, 121.8 mmol) was stirred in an ice-
bath, and methanesulfonyl chloride ꢀ10.2 g, 90 mmol)
was added via a syringe at a rate of 0.23 mL/min.
The reaction was allowed to stirr for 1 h at this
temperature and then quenched with 250 mL of ice-
water. The mixture was washed successively with
1
organic layer was dried over Na SO and concentrated
under vacuum. The crude product was puri®ed by silica
gel chromatography.
7. ꢀa) Majdoub, M.; Loupy, A.; Fl eÁ che, G. Eur.Polym.J. 1994,
30, 1431. ꢀb) Thiem, J.; L uÈ ders, H. Polym.Bull.ꢀBerlin) 1984,
11, 365. ꢀc) Thiem, J.; L uÈ ders, H. Starch/St aÈ rke 1984, 36, 170.
ꢀd) Storbeck, R.; Rehahn, M.; Ballauff, M. Makromol.Chem.
1994, 194, 53. ꢀe) Cognet-Georjon, E.; M e chin, F.; Pascaut,
J. P. Makromol.Chem.Phys. 1995, 196, 3733. ꢀf) Bachmann,
F.; Reimer, J.; Ruppenstein, M.; Thiem J.Macromol.Rapid
Commun. 1998, 19, 21.
.5 M HCl ꢀ200 mL), 10% NaHCO3 ꢀ200 mL). The
2
4
8. Meng, Q.; Thibblin, A. J.Am.Chem.Soc. 1995, 117, 9399.
9
. ꢀa) Bartsch, R. A.; Bunnett, J. F. J.Am.Chem.Soc. 1969, 91,
1376. ꢀb) Veeravagu, P.; Arnold, R. T.; Eigenmann, G. W.
J.Am.Chem.Soc. 1964, 86, 3072.
2
1
1
n-Octyl methanesulphonate: colourless oil. H NMR
ꢀ
200 MHz, CDCl ): d 0.90 ꢀt, 3H, J6.80 Hz), 1.08±1.82
3
ꢀ
m, 12 H), 2.97 ꢀs, 3H), 4.16 ꢀt, 2H, J6.51 Hz).
10. Shaffer, T. D.; Antolin, K.; Percec, V. Makromol.Chem. 1987,
88, 1033.
1
7
.1.3. General procedure for the synthesis of 2. Synthesis
11. ꢀa) Chang, C.; Kiesel, R. F.; Hogen-Esch, T. J.Am.Chem.Soc.
1973, 95, 8446. ꢀb) Pocker, Y.; Ronald, B. P. J.Am.Chem.
Soc. 1978, 100, 2795.
of 2 was performed under microwave irradiation or conven-
tional heating. In a Pyrex cylindrical open reactor adapted to
the Synthewave reactor, 3.42 mmol ꢀ0.5 g) of 1 were mixed
with 10.26 mmol of n-octyl halide, tosylate or mesylate,
1
1
about 15% of water] and 0.5 mL of solvent. The mixture
was then homogenized and submitted to microwave irradia-
tion under mechanical stirring. At the end of irradiation, the
reaction mixture was cooled and extracted with methylene
chloride. The extracts were evaporated under reduced
pressure, analyzed by g.c. ꢀwith internal standard of dioctyl
phthalate). Pure products 2 were isolated by liquid
chromatography on silica gel using pentane/ethyl acetate
as eluant.
12. ꢀa) Epiotis, N. D.; Cherry, W. R.; Shaik, S.; Yates, R.;
Bernardi, F. Topics Current Chem. 1977, 70. ꢀb) Bunnett,
J. F.; Zahler, R. E. Chem.Rev. 1951, 49, 273. ꢀc) Talma,
A. G.; Vossen, H.; Sudh oÈ lter, E. J. R.; Eerden, J.; Reinhoudt,
D. N. Synthesis 1985, 2241. ꢀd) Reinhoudt, D. N.; Jong, F.;
Tomassen, H. P. M. Tetrahedron Lett. 1979, 22, 2067.
13. ꢀa) Danilova, O. I.; Esikova, I. A.; Yu®t, S. S. Izv.Akad.Nauk
SSSR Ser.Khim. 1986, 2422. ꢀb) Yu®t, S. S.; Zinovyev, S. S.
Tetrahedron 1999, 55, 6319. ꢀc) Loupy, A.; Pardo, C.
Synthetic Commun. 1988, 18, 1275.
0.26 mmol of MY, 0.01 mmol ꢀ0.322 g) of TBAB,
0.26 mmol of powdered KOH ꢀ0.665 g) [containing
14. ꢀa) Cohen, S.; Zoran, A.; Sasson, Y. Tetrahedron Lett. 1998,
39, 9815. ꢀb) Starks, C. M. J.Am.Chem.Soc. 1971, 93, 195.
15. Pauling, L. The Chemical Bond, Cornell University Press:
London, 1967.
d-sorbitol 1,4:3,6-dianhydro,2,5-di-O,O-octyl 2: isolated as
a syrup; R 0.42 ꢀpentane/EtOAc 1/1); H NMR ꢀ250 MHz,
16. Handbook of Chemistry and Physics, 57th, CRC Press: Boca
Raton, FL, 1977; pp. F109.
1
f
CDCl ): d 0.90 ꢀt, 6H, H , J7.8 Hz), 1.5±1.15 ꢀm, 20H,
17. Hajek, M., Radoiu, M. Second World Congress on Microwave
and Radio Frequency Processing, Orlando ꢀUSA), April 2±6,
2000. Comm. MWB-CP2-02.
3
14
H ±H ), 1.6 ꢀm, 4H, H ), 3.55 ꢀm, 5H, H H H ), 3.90
9
12
8
7
6a
6b
ꢀ
ꢀ
1
m, 5H, H H H H H ), 4.45 ꢀd, 1H, H , J4.3 Hz), 4.65
2
5
7
1a 1b
3
1
3
dd, 1H, H , J4.85 Hz); C NMR ꢀ62.9 MHz, CDCl ): d
4 3
18. ꢀa) Vidal, T.; Petit, A.; Loupy, A.; Gedye, R. N. Tetrahedron
2000, 56, 5473. ꢀb) Bogdal, D.; Pielichowski, J.; Boron, A.
Synlett 1996, 873. ꢀc) Jinchang, D.; Hangjie, G.; Jinzhu, W.;
Caizhen, L. Synthetic Commun. 1994, 24, 301. ꢀd)
Rechsteiner, B.; Texier-Boullet, F.; Hamelin, J. Tetrahedron
Lett. 1993, 32, 5074. ꢀe) Varma, R. S.; Dahiya, R.; Kumar, S.
Tetrahedron Lett. 1997, 38, 2039.
4.1 ꢀCH ,C-14), 22.7 ꢀCH , C-13), 26.0 ꢀCH , C-12), 29.2
3 2 2
ꢀCH , C-11), 29.4 ꢀCH , C-10), 29.8 ꢀCH , C-9), 32.2 ꢀCH ,
2 2 2 2
C-8), 69.9 ꢀC-7), 71.0 ꢀC-1), 73.5 ꢀC-6), 80.2 ꢀC-4), 80.5 ꢀC-
5
7
1
), 84.5 ꢀC-2), 86.4 ꢀC-3). Anal. Calcd for C H O : C,
22 42 4
1.35; H, 11.35; O, 17.29. Found: C, 71.30; H, 11.46; O,
7.24.