1
HYDROGEN BONDS IN POLYAMINES: H-NMR STUDIES
applied until a dried residue was obtained; it was reduced to
powder in a mortar and the procedure was repeated until no
impurities were detected by thin-layer chromatography. Finally,
it was kept in a desiccator protected from light under dry
[6] M. Adler, M. Marsch, N. S. Nudelman, G. Boche, Angew. Chem. 1999,
38, 1261.
[7] N. S. Nudelman, H. Schulz, J. Chem. Soc. Perkin Trans. 2 1999, 2761.
[
8] N. S. Nudelman, G. Garcia Li n˜ ares, J. Org. Chem. 2000, 65, 1629.
[
9] C. Rodr ´ı guez, A. J. V a´ zquez, N. S. Nudelman, ARKIVOC 2008, 6,
[
42]
nitrogen atmosphere (mp 242–244 8C, lit. 242.8–244.5 8C).
-Dimethylamino-1-propylamine (DMPA) was prepared
from dimethylamine and acrylonitrile adapting known
After two days, the excess of dimethylamine was
distilled off under reduced pressure at 75–77 8C/11 mmHg Torr).
The N,N-dimethylpropanenitrile obtained was reduced with
Na/EtOH. Distillation of the resulting product gave DMPA as a
1
40–151.
3
[10] S. M. R ´ı os, N. S. Nudelman, Environ. Technol. 2008, 29, 23–33.
[11] N. S. Nudelman, S. M. R ´ı os, O. Katusich, J. Phys. Org. Chem. 2008, 21,
329–337.
12] P. Hobza, Z. Havlas, Chem. Rev. 2000, 100, 4253.
13] S. Scheiner, Hydrogen Bonding: A Theoretical Perspective, Oxford
University Press, New York, 1997.
a
[
43]
technique.
[
[
[14] V. Bertolasi, P. Gilli, V. Ferretti, G. Gilli, J. Am. Chem. Soc. 2000, 122,
0405.
[15] I. Alkorta, J. Elguero, O. M o´ , M. Y a´ nez, J. E. Del Bene, Chem. Phys. Lett.
005, 411, 411–415.
1
liquid, which was stored under a nitrogen atmosphere at 5 8C
1
(
1
bp. 133–135 8C). [ H-NMR (CDCl
3
): d ¼1.30 (s, 2H, broad, —NH
2
),
2
.70 (m, 2H, —CH —), 2.31 (s, 6H, CH ), 2.41 (t, 2H, —CH —), 2.84
2 3 2
[16] G. R. Desiraju, Y. Steiner, The Weak Hydrogen Bond in Structural
Chemistry and Biology, Oxford University Press, New York, 1999.
(
t, 2H, —CH
2
—)].
[
17] C. F. Reichardt, Solvents and Solvents Effects in Organic Chemistry, 3rd
edn, Wiley-VCH, Weinheim, 2003.
18] N. S. Nudelman, ANS of amines in aprotic solvents, in The Chemistry of
Amino, Nitroso, Nitro and Related Groups, Ch. 29 (Ed.: S. Patai), Wiley,
London, 1996.
1
,2-Diaminoethane: (EDA, Fluka) was kept overnight over
potassium hydroxide, distilled over zinc powder and then
over sodium; both distillations were carried out at normal
pressure, and the fraction of bp. 116–118 8C was collected (lit.
[
[
44]
1
16.5 8C).
It was kept in a desiccator protected from light.
[19] C. E. S. Alvaro, N. S. Nudelman, ARKIVOC 2003, X, 95–106.
[20] N. S. Nudelman, C. E. S. Alvaro, M. Savini, V. Nicotra, J. S. Yankelevich,
Collect. Czech. Chem. Commun. 1999, 64, 1583–1593.
0
4(5)-2 -Aminoethylimidazole (Histamine Base) (Fluka) was used
without any purification and was kept in a desiccator protected
from light.
[
21] C. E. S. Alvaro, N. S. Nudelman, J. Phys. Org. Chem. 2005, 18, 880–885
references cited therein).
[22] P. M. Mancini, A. C. Perez, L. R. Vottero, J. Solution Chem. 2001, 30,
95–707.
(
1-(2-Aminoethyl)piperidine (2-AEPip, Aldrich): the commercial
6
product was kept over sodium strings during several days,
distilled by reduced pressure fractional distillation over zinc powder
and then twice over sodium strings under reduced pressure. The
fraction of 78–80 8C at 20 mmHgTorr was collected. It was kept in a
desiccator under dry nitrogen atmosphere, protected from light,
and it was re-distilled immediately before use.
N-(3-amino-1-propyl)morpholine (3-APMo, Aldrich): the com-
mercial product was kept over sodium strings during several
days, distilled by reduced pressure fractional distillation over zinc
powder and then twice over sodium strings under reduced
pressure. The fraction 96–97 8C at 20 mmHg Torr was collected.
It was kept in a desiccator under dry nitrogen atmosphere,
protected from light, and was re-distilled immediately before
using.
[
23] P. M. Mancini, G. Fortunato, C. Adam, L. R. Vottero, A. J. Terenzani, J.
Phys. Org. Chem. 2002, 15, 258–269.
24] P. M. Mancini, C. Adam, A. C. Perez, L. R. Vottero, J. Phys. Org. Chem.
2000, 13, 221–231.
[
[25] C. Boga, L. Forlani, J. Chem. Soc. Perkin Trans. 2 2001, 1408–1413 (and
references cited therein).
[
26] L. Forlani, C. Boga, M. Forconi, J. Chem. Soc. Perkin Trans. 2 1999,
455–1458.
27] M. Luhmer, K. Bartik, J. Phys. Chem. A 1997, 101, 78.
1
[
[28] A. Ebrahimi, M. Habibi, H. R. Masodi, Chem. Phys. Lett. 2009, 478, 120.
[
[
29] D. R. Bhuvaneshwari, K. P. Elango, J. Mol. Liq. 2008, 143, 147–153.
30] M. Santo, R. Cattana, J. J. Silber, Spectrochim. Acta A 2001, 57,
1541–1553.
[
31] C. N. Rao, T. Pradeep, Chem. Soc. Rev. 1991, 20, 477.
[32] D. R. Bhuvaneshwari, N. Kalaimani, S. Rathinam, Indian J. Chem. 2008,
47A, 1348–1354.
[
33] M. Harati, M. R. Gholami, Int. J. Chem. Kinet. 2005, 37, 90–97.
34] A. Habibi-Yangjeh, Y. Jafari-Tarzanag, A. R. Banaei, Int. J. Chem. Kinet.
[
2
009, 41, 153–159.
Acknowledgements
[
35] C. E. S. Alvaro, A. D. Ayala, N. S. Nudelman, J. Phys. Org. Chem. 2010,
DOI: 10.1002/poc.1712, in press.
36] L. Giacomelli, R. Cattana, J. D. Anunziata, J. J. Silber, M. Hedrera, S.
Salerno, I. Perillo, J. Phys. Org Chem. 1994, 7, 162–168.
The authors gratefully acknowledge financial support from the
Universidad Nacional del Comahue (grant n- I149-UNCo) and
from the National Research Council (CONICET) from Argentine
[
[37] J. Chen, P. G. Willis, S. Parkin, A. Cammers, Eur. J. Org. Chem. 2005,
(
grant n- PIP 6019).
171–178.
[
[
[
38] S. H. Gellman, G. P. Dado, G. B. Liang, B. Adam, J. Am. Chem. Soc. 1991,
13, 1164–1173.
39] J. Kidric, D. Hadzi, D. Kocian, V. Rutar, Org. Magn. Reson. 1981, 15,
–280.
1
REFERENCES
3
40] C. E. S. Alvaro, N. S. Nudelman, Int. J. Chem. Kinet. 2010, 42(12),
[
[
1] M. Drac ´ı nsk y´ , P. Bour, J. Chem. Theory Comput. 2010, 6, 288–299.
2] A. R. Breier, N. S. Nudelman, E. Schapoval, J. Pharm. Biomed. Anal.
008, 46, 250–257.
735–742.
[41] F. Bergero, C. E. S. Alvaro, N. S. Nudelman, S. Ramos de Debiaggi, J.
Mol. Struct. (Theochem) 2009, 896, 18–24.
2
[
[
[
3] B. Casta n˜ eda, W. Ortiz Cala, L. Millan, C. Gallardo Cabrera, N. S.
Nudelman, J. Phys. Org. Chem. 2009, 22, 1523–1531.
4] C. Garcia, N. S. Nudelman, M. Steppe, E. Schapoval, J. Pharm. Biomed.
Anal. 2008, 46, 88–93.
5] N. S. Nudelman, H. Schulz, G. Garcia Li n˜ ares, A. Bonatti, G. Boche,
Organometallics 1998, 17, 146.
[42] N. Andrade-L o´ pez, A. Ariza-Castolo, R. Contreras, A. V a´ squez-Olmos,
N. Barba Behrens, H. Tlahuext, Heteroatom Chem. 1997, 8, 397–410.
[43] A. Vogel, Practical Organic Chemistry, 5th edn, Longman, New York,
USA, 1999, p. 564.
[44] D. R. Lide (Ed.), Handbook of Chemistry and Physics, 79th edn, CRC
Press, Gaitherburg, USA, 1998, p. 292.
J. Phys. Org. Chem. 2011, 24 1067–1071
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