5
48
M. Kwiatkowska et al.
to the cycloadducts 3 and 4. A Knauer system (Smartline
000 HPLC pump and Smartline 4000 thermostat) equipped
with Smartline 2500 UV–Vis detector and LiChrospher 100-
0 RP column (4 9 240 mm i.d.) was applied for analysis.
2. Ono N (2001) In: The nitro group in organic synthesis. Wiley,
New York
1
3
. Baer HH, Urbas L (1970) In: The chemistry of nitro and nitroso
groups, Part 2, Wiley, New York
1
4. Jasi n´ ski R, Kwiatkowska M, Bara n´ ski A (2007) Wiad Chem
67:485
3
Methanol–water (50:50 v/v) at flow rate of 1.3 cm /min was
used as the eluent. Analyses were carried out at 25 °C and
k = 254 nm. At these conditions both cycloadducts had the
same retention times (t = 11.3 min). The starting reaction
mixtures were prepared by adding a weighed quantity of
suitable (E)-2-phenylnitroethene to the solution of freshly
distilled cyclopentadiene in dry nitromethane. The initial
5
6
. Bara n´ ski A (2002) J Phys Org Chem 15:78
. Jasi n´ ski R, W a˛ sik K, Mikulska M, Bara n´ ski A (2009) J Phys Org
Chem 22:717
7. Jasi n´ ski R, Bara n´ ski A (2008) Collect Czech Chem Commun
73:649
8
. Jasi n´ ski R, Jasi n´ ska E, Bara n´ ski A (2008) Chem Heterocyclic
Comp 44:735
. Jasi n´ ski R, Bara n´ ski A (2006) Pol J Chem 80:1493
9
3
concentration of the latter reactant was 0.05 mol/dm ,
10. Kwiatkowska M (2008) PhD thesis, Cracow University of
Technology, Cracow
11. Zewail HA (1996) J Phys Chem A 100:12701
2. Cramer CJ (2002) Essentials of computational chemistry. Wiley,
Chichester
13. Meander L, Saunders WH (1980) Reaction rates of isotopic
molecules. Wiley, New York
14. Mattsson O, Westway KC (1998) Adv Phys Org Chem 31:143
5. Denmark SC, Thorarensen A (1996) Chem Rev 96:137
6. Wade PA, Murray JK, Shah-Patel S, Caroll PJ (2002) Tetrahe-
dron Lett 43:2585
whereas the former one was always used in 20–22-fold molar
3
excess. The mixtures were placed in ampoules of 1 cm
1
capacity and thermostated at 70 ± 0.2 °C. During kinetic
runs, the ampoules were taken periodically from the ther-
mostat and immediately cooled in an ice bath. Samples of
3
50 mm were taken from the ampoules with a microsyringe
2
1
1
3
and were diluted with 1,000 mm methanol. The solutions
were analyzed by HPLC at analytical wavelength 210 nm. It
was found that, for this wavelength, the Bouguer–Beer plot
was linear within the concentration range studied. Second-
order rate constants ktotal (Table 1) were obtained by a routine
method [34]. Control experiments showed that, under the
conditions used for the kinetic measurements, the concen-
trations of 3 and 4 were measured with an error less than 3%.
After completion of the reaction, the ratio of the cycloadducts
in product mixture, c = [3]/[4], was determined by HPLC.
The analyses were carried out at 5 °C, using LiChrospher
17. Wade PA, Murray JK, Shah-Patel S, Le HT (2002) Chem
Commun 1090
1
8. Sustmann R, Tappanchai S, Bandmann H (1996) J Am Chem Soc
18:12555
1
19. Kataoka F, Shimizu N, Nishida S (1980) J Am Chem Soc
102:711
2
0. Vassilikoginnakis G, Orfanopoullos M (1998) Tetrahedron Lett
9:8891
3
2
1. Jasi n´ ski R, Kwiatkowska M, Bara n´ ski A (2009) J Mol Struct
(TheoChem) 910:80
22. Arroyo P, Picher MT, Domingo LR (2004) J Mol Struct (Theo-
Chem) 709:45
1
00-5RPcolumn(4 9 240 mmi.d.), methanol–water(55:45
2
3. Arroyo P, Picher MT, Domingo LR, Terrier F (2005) Tetrahedron
1:7365
3
v/v)mixtureaseluent, andeluentflowrateof0.5 cm /min. At
these conditions, thepeaks corresponding to the cycloadducts
were clearly separated [t(3) = 203 min, t(4) = 224 min].
The ktotal and c values were converted to the rate constants kA
6
24. Domingo LR, Aurell MJ, Kneetman MN, Mancini PM (2008)
J Mol Struct (TheoChem) 853:68
5. Steglenko DV, Kletsky ME, Kurbatov SV, Tatarov AV, Minkin
VI, Goumont R, Terrier F (2009) J Phys Org Chem 22:298
6. TYa Paperno, Perekalin VV (1972) Infrakrasnye Spektry Nitro-
soedinenii, Izd. GPI im. Gertsen’a, Leningrad
2
2
2
and k (Table 2) according to the following formulas:
B
kA ¼ c ktotal=ðc þ 1Þ kB ¼ ktotal=ðc þ 1Þ:
7. Streitwieser A, Jagow RH, Fahey RC, Suzuki S (1958) J Am
Chem Soc 80:2326
2
2
8. O’Leary MH, Marlier JF (1978) J Am Chem Soc 100:2582
9. Jasi n´ ski R, Bara n´ ski A (2010) Czasopismo Techn. PK (Chemia)
Acknowledgments Generous allocation of computing time by the
regional computer center ‘‘Cyfronet’’ in Cracow (grant MNiI/
SGI2800/PK/053/2003) and financial support from the Polish Min-
istry of Science and Higher Education (grant C2/263/DS/2008) are
gratefully acknowledged.
(
in press)
3
3
0. Ciosłowski J, Bara n´ ski A, Ju sˇ ka T (1986) Tetrahedron 42:4549
1. Vogel AI, Furniss BS, Hannaford AJ, Smith PWG, Tatchell AR
(1996) Textbook of practical organic chemistry, 5th edn. Wiley,
New York
3
2. Bara n´ ski A, Lyubimtsev A, Jasi n´ ski R, Kwiatkowska M (2008)
Pol J Chem 82:1037
33. Kistiakowsky GB, Lacher JR (1936) J Org Chem 58:123
References
3
4. Schwietlick K (1971) Kinetische Metoden zur Untersuchung von
Reaktionsmechanismen. VEB Deutscher Verlag der Wissens-
chaften, Berlin
1
. Perekalin VV, Lipina ES, Berestovitskaya VM, Efremov DA
1994) Nitroalkenes; conjugated nitro compounds. Wiley,
Chichester
(
1
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