4714
C. Koopmans et al. / Tetrahedron 62 (2006) 4709–4714
polyoxazoline and poly(phenylene vinylene) under usage of
metal catalysts can be provided.
124.22–129.37 (Ar), 111.23 (vinyl), 69.69 (O–CH2), 32.02
(CH2–CH2–CH2), 19.91 (CH2–CH3), 14.42 ppm (CH3).
4.2.3. 1-Oxa-2-oxocyclooctanone (14) and 1-oxa-2-oxocy-
clononanone (15). m-Chloroperoxy benzoic acid with 30%
water content (5.2 g, 20 mmol) was added to a solution of
the cyclic ketone (12 or 13) (20 mmol) in 20 mL methylene
chloride. The mixtures were refluxed for 3 and 4 h, respec-
tively. For kinetic measurements samples were taken every
hour. MW-assisted reactions were performed under 100 W
irradiation and else same conditions.
4. Experimental
4.1. Materials and methods
p-Divinylbenzene was synthesized and purified according to
literature procedures.22,23
All reagents used in our experiments were of analytical
grade and were used without further purification.
1
Compounds 14: H NMR (500.13 MHz, CDCl3): d¼4.45–
4.32 (t, 2H, OCH2), 2.65–2.55 (t, 2H, COCH2), 1.95–
1.54 ppm (m, 8H); 15: H NMR (200.13 MHz, CDCl3):
1
The identity of the synthesized compounds was confirmed by
1
d¼4.38–4.29 (t, 2H, OCH2), 2.38–2.28 (t, 2H, COCH2),
mass spectrometry, NMR, and IR measurements. H NMR
and 13C NMR were performed using a Bruker Advance
DRX 500 spectrometer at 500.13 and 200.13 MHz for proton
and 125.77 MHz for carbon in CDCl3 as solvent. The d-scale
relative to TMS was calibrated to the deuterium signal of the
solvent as internal standard. Infrared spectra were recorded
on a Nicolet 5SXB FTIR spectrometer. Size exclusion chro-
matography (SEC) was performed on a SEC-system consist-
ing of a Waters 486 tunable absorbance detector at 275 nm
and a Waters 410 differential refractometer, using THF as
eluent. The system was calibrated with polystyrene standards
with a molecular weight range from 580 to 1,186,000 D. The
flow rate was 1 mL/min. Polymer solution [100 mL of
a 0.125% (w/w)] was injected to a HEMA-column-combina-
2.00–1.32 ppm (m, 6H).
References and notes
1. Bogdal, D.; Penczek, P.; Pielichowski, J. Adv. Polym. Sci. 2003,
163, 193.
2. Wiesbrock, F.; Hoogenboom, R.; Schubert, U. S. Macromol.
Rapid Commun. 2004, 25, 1739.
3. Sinnwell, S.; Schmidt, A. M.; Ritter, H. J. Macromol. Sci., Pure
Appl. Chem. 2006, A43, 469.
4. Sinnwell, S.; Ritter, H. Macromol. Rapid Commun. 2005, 3, 160.
5. Iannelli, M.; Ritter, H. Macromol. Chem. Phys. 2005, 206, 349.
6. Klink, M.; Kolb, U.; Ritter, H. e-Polymers 2005, no. 69.
7. Sonche, J.-S. Mol. Divers. 2003, 7, 233.
˚
tion consisting of a pre-column of 40 A and main columns of
˚
40, 100, and 300 A porosities. For MW-assisted synthesis
8. Larhed, M.; Moberg, C.; Hallberg, A. Acc. Chem. Res. 2002,
35, 717.
9. Nehls, B. S.; Asawapirom, U.; Fuldner, S.; Preis, E.; Farrell, T.;
¨
Scherf, U. Adv. Funct. Mater. 2004, 14, 352.
a monomodal microwave (CEM-Discover) equipped with
an infrared pyrometer with maximum operation power of
300 W was used.
10. Larhed, M.; Hallberg, A. J. Org. Chem. 1996, 61, 9582.
11. Iannelli, M.; Alupei, V.; Ritter, H. Tetrahedron 2005, 61, 1509.
12. Luin, C.; Langlois, V.; Guerin, P.; Le Borgne, A. Macromol.
Rapid Commun. 1999, 20, 289.
4.2. Synthesis
4.2.1. 1,4-Diiodo-2,5-dibutoxybenzene (4). 1,4-Diiodo-2,5-
dibutoxybenzene was synthesized according to literature
procedures shown in Scheme 1.24
´ ˆ
13. Dubois, P.; Jacobs, C.; Jerome, R.; Teyssie, P. Macromolecules
´
1991, 24, 2266.
14. Gopp, U.; Sandner, B.; Schoch, R.; Schlothauer, K.; Pasch, H.;
¨
4.2.2. Poly(2,5-dibutoxy-1,4-phenylenevinylene) (6). Tri-
butylamine (0.53 mL, 2.2 mmol) was added to a solution
of 1,4-diiodo-2,5-dibutoxybenzene (4) (474 mg, 1 mmol),
p-divinylbenzene (144 mL, 1 mmol), Palladium-(II)-acetate
(9 mg, 0.04 mmol), and tri-(o-tolyl)phosphine (61 mg,
0.2 mmol) in 5 mL 1,4-dioxane. For a series of kinetics
5 mL samples were taken from a 70 mL stock solution.
MW-assisted reactions were irradiated to reflux at 300 W in
a mono-mode microwave reactor under nitrogen atmosphere.
Reaction mixture in oil bath was heated up to reflux under
nitrogen atmosphere. The reaction mixture (5 mL each)
was poured into 20 mL of methanol. The precipitated orange
polymer was collected by filtration, washed several times
with 20 mL of methanol, and dried for 12 h under vacuum.
Ghahary, R. Macromol. Symp. 1998, 130, 113.
15. Kagiya, T.; Narisawa, S.; Maeda, T.; Fukui, K. J. Polym. Sci.,
Part B: Polym. Lett. 1966, 4, 441.
16. Levy, A.; Litt, M. J. Polym. Sci., Part B: Polym. Lett. 1967, 5,
881.
17. Kobayashi, S.; Uyama, H. J. Polym. Sci., Part A: Polym. Chem.
2002, 40, 192.
18. Braun, D.; Cherdron, H.; Ritter, H. Polymer Synthesis: Theory
and Practice, 3rd ed.; Springer: Berlin, 2001; p 166 ff.
19. Fouque, E.; Rousseau, G. Synthesis 1989, 9, 661.
20. Hayes, B. L. Microwave Synthesis: Chemistry at the Speed of
Light; CEM: Matthews, USA, 2002.
21. Microwave Chemistry; Introductory page; http://www.
22. Campbell, T. W.; McDonald, R. N. J. Org. Chem. 1959, 24,
1246.
23. Hauser, Ch. F.; Brooks, T. W.; Miles, M. L.; Raymond, M. A.;
Butler, G. B. J. Org. Chem. 1963, 28, 372.
24. Bao, Z.; Chen, Y.; Cai, R.; Yu, L. Macromolecules 1993, 26,
5281.
FTIR (diamond): 2955 (nC–H), 2929 (nꢁCH ), 2867 (nꢁCH ꢁ),
3
2
1594(nAr), 1495(nAr), 1466(dCH ꢁCH ), 1420, 1200(n–C–O–C),
2
3
1027, 960 cmꢁ1
(vinyl), 4.03 (–OCH2), 0.93–1.81 ppm (polymer backbone);
;
1H NMR (CDCl3): d¼7.47 (Ar), 7.10
13C NMR (CDCl3): d¼151.57 (O–C–Ar), 138.74 (vinyl),