1212
PONOMAREV et al.
by double distillation, bp 42 44 C/230 mm Hg, nD20
1.4192. 1,3,5-Triphenylverdazyl was prepared and
purified as described in [73]. The majority of alcohols
were dried by prolonged refluxing over calcined CaO,
distilled, and fractionated from sodium metal. Allyl
alcohol was dried over calcined K2CO3. Viscous hex-
anol and octanol were kept at 100 C over sodium
metal grains and fractionated in a vacuum. Aprotic
solvents were dried and fractionated.
42.6, 0.0518; 47.3, 0.0784; 53.0, 0.100; 60.0, 0.180.
PhBr. 25.5, 0.0127; 30.4, 0.0248; 33.3, 0.0292; 37.9,
0.0342; 40.9, 0.0410; 52.5, 0.137. PhCl. 29.4, 0.0844;
33.4, 0.0114; 38.0, 0.0198; 50.4, 0.0477; 55.5, 0.0710.
Dioxane. 28.8, 0.00424; 34.0, 0.00613; 40.1, 0.0118;
46.5, 0.0184; 50.9, 0.0262. THF. 34.0, 0.00548; 37.2,
0.00801; 45.2, 0.0161; 54.1, 0.0349. AcOEt. 40.8,
0.00321; 44.4, 0.00474; 52.2, 0.0135; 56.0, 0.0179;
60.2, 0.0233.
Kinetic experiments were performed in a tempera-
ture-controlled cell of an SF-26 spectrophotometer.
The substrate concentration in kinetic experiments
was 0.01 0.5 M, and the verdazyl indicator concen-
Calculation by Eqs. (6) (8) was performed using the
EXCEL 97 program package, confidence level 95%.
REFERENCES
4
tration, (1 3) 10 M. The substrate conversion in
kinetic experiments was 0.001 1%, and the indicator
conversion, 5 50%. The rate constants k were deter-
mined with an accuracy of 3%.
1. Ponomarev, N.E., Zaliznyi, V.V., and Dvorko, G.F.,
Zh. Obshch. Khim., 2005, vol. 75, no. 10, p. 1593.
2. Ponomarev, N.E., Zaliznyi, V.V., and Dvorko, G.F.,
Zh. Obshch. Khim., 2005, vol. 75, no. 9, p. 1503.
Below are given the solvent, temperature ( C), and
1
k
107 (s ). MeOH. 11.6, 283; 16.7, 605; 21.2,
3. Sneen, R.A., Carter, J.V., and Kay, P.S., J. Am. Chem.
Soc., 1966, vol. 88, no. 11, p. 2594.
1050; 25.0, 1470; 25.6, 1460; 30.2, 2560. Allyl alco-
hol. 22.0, 452; 25.0, 643; 27.0, 825; 32.4, 1310; 38.0,
2840; 46.2, 4800. EtOH. 18.5, 146; 22.0, 228; 25.0,
328; 26.7, 464; 32.6, 779; 39.8, 1380. BuOH. 22.0,
40.2; 25.0, 58.4; 25.5, 60.2; 30.6, 123; 36.3, 192;
41.5, 312. i-BuOH. 23.5, 53.3; 25.0, 57.4; 28.5, 71.0;
38.5, 215; 46.2, 445; 51.2, 595. PentOH. 22.0, 23.9;
25.0, 35.1; 27.2, 48.3; 33.7, 93.3; 40.8, 201; 46.33,
383. i-PrOH. 25.0, 30.5; 27.0, 39.1; 29.1, 39.3; 35.5,
65.8; 39.0, 87.7; 47.5, 138. HexOH. 19.3, 13.4; 22.0,
19.8; 25.0, 29.7; 28.7, 46.4; 34.8, 123; 41.3, 214.
Cyclohexanol. 25.0, 24.2; 26.1, 28.2; 33.3, 71.0; 40.5,
152; 48.4, 458. OctOH. 22.4, 16.0; 25.0, 22.4; 27.5,
31.2; 32.5, 54.4; 38.3, 120.0; 42.3, 170.0. 2-BuOH.
22.0, 13.6; 25.0, 18.8; 29.2, 28.7; 38.1, 80.5; 42.5,
113. t-BuOH. 22.0, 2.50; 25.0, 3.57; 27.5, 4.77; 31.0,
7.18; 34.8, 11.1; 39.7, 20.8. t-PentOH. 22.0, 1.15;
25.0, 1.67; 28.4, 2.38; 35.4, 4.71; 43.0, 7.87; 48.6,
11.1. Sulfolane. 25.3, 8.22; 29.9, 18.3; 32.7, 23.3;
36.7, 34.9; 40.9, 55.8. Propylene carbonate. 22.4,
5.26; 27.1, 8.99; 32.4, 18.6; 36.2, 27.3; 40.8, 56.9.
-Butyrolactone. 22.0, 2.21; 30.6, 8.02; 37.0, 17.7;
43.5, 33.5; 52.0, 61.8. MeCN. 22.0, 1.80; 25.0, 2.75;
26.3, 3.72; 32.6, 7.58; 39.8, 19.7; 47.0, 42.8. PhNO2.
18.0, 0.0758; 21.6, 0.104; 25.0, 0.174; 27.2, 0.249;
33.8, 0.515; 39.4, 0.808. PhCN. 21.4, 0.0775; 24.4,
0.134; 30.6, 0.261; 35.3, 0.417; 39.8, 0.839. PhCOMe.
20.5, 0.0589; 25.0, 0.109; 25.2, 0.118; 29.3, 0.193;
34.6, 0.315. 1,2-Dichloroethane. 17.0, 0.100; 31.2,
0.167; 40.4, 0.377; 48.5, 0.866; 56.3, 0.945. Acetone.
25.0, 0.0497; 29.5, 0.0686; 38.4, 0.137; 44.0, 0.179;
50.4, 0.299. MeCOEt. 23.1, 0.0379; 27.5, 0.0598;
32.6, 0.0996; 39.2, 0.155; 53.5, 0.642. Cyclohexan-
one. 22.3, 0.0341; 28.4, 0.0674; 33.7, 0.0973; 41.2,
0.200; 47.9, 0.342. 1,2-Dichlorobenzene. 34.8, 0.0349;
4. Dvorko, G.F., Ponomarev, N.E., and Ponomare-
va, E.A., Zh. Obshch. Khim., 1999, vol. 69, no. 11,
p. 1835.
5. Dvorko, G.F., Ponomareva, E.A., and Ponoma-
rev, M.E., J. Phys. Org. Chem., 2004, vol. 17, no. 4,
p. 825.
6. Reichardt, Ch., Solvents and Solvent Effects in Or-
ganic Chemistry, Weinheim: VCH, 1988.
7. Dvorko, G.F., Pervishko, T.L., Golovko, N.I., Va-
sil’kevich, A.I., and Ponomareva, E.A., Zh. Org.
Khim., 1993, vol. 29, no. 9, p. 1805.
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p. 2267.
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Zh. Obshch. Khim., 2002, vol. 72, no. 10, p. 1644.
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12. Buncel, E., Millington, J.P., and Wiltshire, J.F., Can.
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13. Quameneur, F., Baiou, B., and Kerfanto, M., C. R.
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