Molecules 2000, 5
1249
NMR data - [Note: all nitroxides were reduced to hydroxylamines for NMR analysis with 1.1
equivalents Na S O in a 1:1 mixture of D O:d -acetone.]
2
2
4
2
6
1
Carboxylic acid 1: H-NMR (1:1 d -acetone, D 2ꢀꢁ/ ppm 1.57 (s, 6 H, 2 -CH ), 1.67 (s, 6 H, 2 -
6
2
3
1
3
CH ), 6.52 (s, 1H, =CH-); C-NMR (1:1 d -acetone, D 2ꢀꢁ/ ꢂꢃꢄꢅꢃꢁꢆꢂꢁ&ꢇꢁꢂꢁꢈ&+ ), 27.35 (2 C, 2 -CH ),
3
6
2
3
3
6
8.36 (1 C, quaternary), 70.87 (1C, quaternary), 137.0 (=C-CO H), 148.8 (=CH-), 167.4 (=C-CO H).
2 2
1
Alcohol 2: H-NMR (1:1 d -acetone, D 2ꢀꢁ/ ppm 1.45 (s, 6 H, 2 -CH ), 1.47 (s, 6 H, 2 -CH ), 4.31
6
2
3
3
1
3
(
s, 1 H, -CH -), 4.32 (s, 1 H, -CH -), 5.81 (s, 1H, =CH-); C-NMR (1:1 d -acetone, D 2ꢀꢁ/ ꢂꢉꢄꢊꢋꢁꢆꢂꢁ&ꢇ
2
2
6
2
2
1
-CH ), 24.80 (2 C, 2 -CH ), 58.21 (1 H, -CH -OH), 70.13 (1 C, quaternary), 72.20 (1C, quaternary),
3 3 2
28.5 (=C-CH OH), 144.5 (=CH-).
2
1
Aldehyde 3: H-NMR (1:1 d -acetone, D 2ꢀꢁ/ SSPꢅꢄꢋꢋꢁꢆVꢇꢁꢅꢂꢁ+ꢇꢁꢋꢁꢈ&+ ), 7.11 (s, 1H, =CH-), 9.69
6
2
3
1
3
(
-CHO); C-NMR (1:1 d -acetone, D Oꢀꢁꢁ/ ppm 24.37 (2 C, 2 -CH ), 24.52 (2 C, 2 -CH ), 68.47 (1 C,
6
2 3 3
quaternary), 68.58 (1C, quaternary), 146.31 (=C-CHO), 156.66 (=CH-), 191.02 (-CHO).
1
Mixed anhydride 4: H-NMR (1:1 d -acetone, D 2ꢀꢁ/ ppm 1.473 (s, 6 H, 2 -CH ), 1.51 (t, 3H, -
6
2
3
CH CH , J = 7.1 Hz), 1.55 (s, 6 H, 2 -CH ), 4.42 (q, 2 H, -OCH CH , J = 7.1 Hz), 6.92 (1H, =CH-).
2
3
3
2
3
1
Ester 7: H-NMR (1:1 d -acetone, D 2ꢀꢁ / ppm 1.47 (s, 6H, 2-CH ), 1.50 (t, 3H, J=7.1 Hz,
6
2
3
1
3
CH CH O), 1.54 (s, 6H, 2-CH ), 4.41 (q, 2H, J=7.1 Hz, CH CH O), 6.91 (s, 1H, CH); C-NMR (1:1
3
2
3
3
2
d -acetone, D 2ꢀꢁ / ppm 13.68 (CH CH O), 24.32 (2 C, 2 -CH ), 24.41 (2 C, 2 -CH ), 60.98
6
2
3
2
3
3
(
CH CH O), 68.05 (1 C, quaternary), 69.72 (1 C, quaternary), 136.7 (=C-CO ), 146.6 (=CH-), 164.8 (-
3
2
2
COOEt).
References
1
2
. Strobel, O. K.; Kryak, D. D.; Bobst, E. V.; Bobst, A. M. Preparation and Characterization of Spin-
Labeled Oligonucleotides for DNA Hybridization. Biocon. Chem. 1991, 289-95.
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Dynamics: Synthesis, Structure and Dynamics of Site and Sequence Specifically Spin- Labeled
DNA. Biochemistry 1989, 28, 9484-9495.
3
4
. Rozantsev, E. G. Synthesis of Some Stable Radicals and the Most Important Intermediates. In:
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Hydroxymethyl-2,2,5,5-tetramethyl-2,5-dihydropyrrole-1-oxyl and 3-Formyl Derivatives. Synthesis
1
980, 911-914.
5
6
. Griffith, O. H.; Keana, J. F. W.; Noall, D. L.; Ivey, J. L. Nitroxide Mixed Carboxylic-carbonic Acid
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