Novel 1,10-diaza-18-crown-6 derivatives

Article abstract of DOI:10.1007/s11172-014-0507-9

Reaction of 1,10-bis(methoxymethyl)-1,10-diaza-18-crown-6 (1) with trimethylsilyl azide resulted in hitherto unknown 1,10-bis(azidomethyl)-1,10-diaza-18-crown-6 (2) and novel ionic compound 1,10-bis(azide anion)-1,10-dihydro-1,10-diaza-18-crown-6 (3). Com

Full text of DOI:10.1007/s11172-014-0507-9

Russian Chemical Bulletin, International Edition, Vol. 63, No. 3, pp. 772—774, March, 2014
772
Novel 1,10ꢀdiazaꢀ18ꢀcrownꢀ6 derivatives
R. G. Kostyanovsky,a K. A. Lyssenko,b O. G. Nabiev,a G. K. Kadorkina,a and I. I. Chervina
aN. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences,
4 ul. Kosygina, 119991 Moscow, Russian Federation.
Eꢀmail: kost@chph.ras.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Eꢀmail: kostya@xrlab.ineos.ac.ru
Reaction of 1,10ꢀbis(methoxymethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (1) with trimethylsilyl azide
resulted in hitherto unknown 1,10ꢀbis(azidomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (2) and novel ionic
compound 1,10ꢀbis(azide anion)ꢀ1,10ꢀdihydroꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (3). Compound 2 reꢀ
acted with dimethyl acetylenedicarboxylate to give 1,10ꢀbis(4,5ꢀdimethoxycarbonyltriazoloꢀ
methyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (4). Carbamoylation of 1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (5) with optiꢀ
cally active ꢀphenylethyl amine yielded optically active 1,10ꢀbis(ꢀphenylethylcarbamoyl)ꢀ
1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (6).
Key words: 1,10ꢀdiazaꢀ18ꢀcrownꢀ6, 1,10ꢀbis(methoxymethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6,
1,10ꢀbis(azidomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6, 1,10ꢀbis(azide anion)ꢀ1,10ꢀdihydroꢀ1,10ꢀdiazaꢀ
18ꢀcrownꢀ6, 1,10ꢀbis(4,5ꢀdimethoxycarbonyltriazalomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6, triꢀ
methylsilyl azide, aminomethylꢀsubstituted triazoles, dimethyl acetylenedicarboxylate.
Scheme 1
Earlier, we developed synthetic procedures towards aziꢀ
doꢀ and cyanomethylamines by the reaction of alkoxyꢀ
methylamines with trimethylsilyl azide (TMSN3) or triꢀ
methylsilyl cyanide (TMSCN). For the compounds synꢀ
thesized, structures and anomeric effects in crystalline state
and gaseous phase were studied. Novel fragmentation of
azidomethoxymethyldimethylamine and novel rearrangeꢀ
ment of triazolylmethylamines were found. Cycloaddition
of azidomethylamines to dimethyl acetylenedicatboxylate
(DMAD) resulted in hitherto unknown aminomethylꢀsubꢀ
stituted triazoles, and their basedꢀcatalyzed isomerization
were studied.1
In the present work, we describe the reactions of
TMSN3 with 1,10ꢀbis(methoxymethyl)ꢀ1,10ꢀdiazaꢀ18ꢀ
crownꢀ6 (1) and 1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (5) with opticalꢀ
ly active ꢀphenylethyl isocyanate.
Compound 1 reacts with TMSN3 in diethyl ether at
room temperature to give 1,10ꢀbis(azidomethyl)ꢀ1,10ꢀdiꢀ
azaꢀ18ꢀcrownꢀ6 (2). Novel ionic compound 1,10ꢀbis(azide
anion)ꢀ1,10ꢀdihydroꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (3) was synꢀ
thesized by refluxing compound 2 in aqueous MeOH for
2 h with the subsequent keeping of the reaction mixture at
–2 C for 24 h (Scheme 1).
Azide anion, one of the wellꢀstudied pseudohaloꢀ
genides, attracts considerable attention from organic and
physical organic chemists.2 Covalently bound azide groups
do not prone to participate in intramolecular interactions;
at the same time, the role of the uncoordinated azide anꢀ
N3– = N–=N+=N–
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0772—0774, March, 2014.
1066ꢀ5285/14/6303ꢀ0772 © 2014 Springer Science+Business Media, Inc.

Novel derivatives of 1,10ꢀdiazaꢀ18ꢀcrownꢀ6
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 3, March, 2014
773
ion in the crystal packing and the intermolecular contact
formation is not almost studied, since the compounds bearꢀ
ing this species in a free state are poorly available.* Weak
interactions of the coordinated azide ions play an imporꢀ
tant role in the crystal packing of metal complex comꢀ
pounds and the free azide anion is the best species for their
investigation.
We also studied carbamoylation of 1,10ꢀdiazaꢀ18ꢀ
crownꢀ6 (5) with optically active ꢀphenylethyl isocyanꢀ
ate. This reaction under mild conditions affords optically
active 1,10ꢀbis(ꢀphenylethylcarbamoyl)ꢀ1,10ꢀdiazaꢀ18ꢀ
crownꢀ6 (6) in excellent yield (Scheme 3).
Scheme 3
The azide group, a promising building block for suꢀ
pramolecular systems, was studied by Xꢀray diffraction in
both coordinated and uncoordinated anionic states on the
example of compound 3.2 Xꢀray diffraction of compound 3
reveals that the diprotonated crown ether cation forms
hydrogen bonds with two uncoordinated azide anions. Reꢀ
finement and analysis of the experimental electron density
distribution show that along with formation of the strong
hydrogen bonds, the azide anion participates in several
weak C—H…N interactions. A comparison of the experiꢀ
mental and calculated data allows us to develop a general
approach to the description of the role of the azide anion
in the crystal packing, which links the integrated charge of
the terminal atoms of the azide anion with their ability to
participate in nonvalent and coordination interactions.2
1
Structure of compound 3 is also confirmed by H NMR
spectroscopy (see Experimental).
1,10ꢀBis(azidomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (2) reꢀ
acts with dimethyl acetylenedicarboxylate (DMAD) to
give triazole derivative, 1,10ꢀbis(4,5ꢀdimethoxycarbonylꢀ
triazolꢀ2ꢀylmethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (4) (Scheme 2).
Similar cycloaddition accompanied the reaction of azidoꢀ
methylamines with DMAD.1 In contrast to cycloaddition
of azidomethylamines to DMAD, in the reaction of comꢀ
pound 2 with DMAD no isomerization of the triazole
derivative occurs; therefore, the reaction is performed withꢀ
out base addition.
In summary, in the present work ionic compound
1,10ꢀbis(azide anion)ꢀ1,10ꢀdihydroꢀ1,10ꢀdiazaꢀ18ꢀ
crownꢀ6 (3) was first synthesized by the reaction of novel
crown ether, e.g., 1,10ꢀbis(azidomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀ
crownꢀ6 (2), with trimethylsilyl azide (TMSN3).
Experimental
Starting compounds, 1,10ꢀbis(methoxymethyl)ꢀ1,10ꢀdiazaꢀ
18ꢀcrownꢀ6 (1), 1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (5), trimethylsilyl azide
(TMSN3), dimethyl acetylenedicarboxylate (DMAD), and
ꢀphenylethyl isocyanate, are commercially available. 1H NMR
spectra were recorded on a Bruker WMꢀ400 spectrometer
(400.13 MHz) in CDCl3 or DMSOꢀd6 relatively to the residual
solvent signal (H 7.26 for CDCl3 and H for DMSOꢀd6).
The optical rotations were measured with a POLAMAT A
polarimeter (Carl Zeiss JENA). Melting points were determined
on a Stuart Scientific Melting point apparatus SMP3 (Great
Britain) in sealed capillaries. Microanalyses were performed on
Perkin Elmer 2400 CHN elemental analyzer.
Scheme 2
1,10ꢀBis(azidomethyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (2). To a soluꢀ
tion of compound 1 (0.77 g, 2.2 mmol) in anhydrous diethyl
ether (3 mL), trimethylsilyl azide (0.51 g, 4.4 mol) was slowly
added at 20 C. The reaction mixture was kept for 12 h at room
temperature, the crystals formed were collected and crystallized
from methanol—diethyl ether (1 : 1) to give compound 2 in the
1
yield of 0.74 g (90%), m.p. 129—131 C. H NMR (CDCl3),
: 2.98 (t, 8 H, 4 CH2N, 3J = 5.6 Hz); 3.69 (s, 8 H, 2 O(CH2)2O);
3
3.76 (t, 8 H, 4 CH2O, J = 5.6 Hz); 4.55 (s, 4 H, 2 NCH2N3).
Found (%): C, 45.13; H, 7.74; N, 30.23. C14H28N8O4. Calculatꢀ
ed (%): C, 45.16; H, 7.53; N, 30.11.
1,10ꢀBis(azide anion)ꢀ1,10ꢀdihydroꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6 (3).
Compound 2 (0.372 g, 1 mmol) was refluxed in MeOH for 2 h
* Cambridge structural database (CSD version 5.30, November
2008 with 3 updates) contains structures of 43 organic comꢀ
pounds bearing the azide anions.

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Russ.Chem.Bull., Int.Ed., Vol. 63, No. 3, March, 2014
Kostyanovsky et al.
and then kept at –2 C for 20 h. Compound 3 was obtained in the
yield of 0.32 g (92%), crystals, m.p. 142—144 C. 1H NMR
(DMSOꢀd6), : 3.16 (t, 8 H, 4 CH2N, 3J = 6.2 Hz); 3.58 (s, 8 H,
was added and the reaction mixture was kept at 20 C for 12 h.
The solvent was removed in vacuo, the residue was crystallized
from diethyl ether to give compound 6 in the yield of 1.63 g
(96%), crystals, m.p. 130—131 C, []D +8.35 (c 1.5, MeOH).
1H NMR (CDCl3), : 1.43 (d, 6 H, 2 CH3CH, 3J = 6.7 Hz); 3.46
(t, 8 H, 4 CH2N, 3J = 6.7 Hz); 3.53 (s, 8 H, 2 O(CH2)2O); 3.62
3
2 O(CH2)2O); 3.71 (t, 8 H, 4 CH2O, J = 6.2 Hz). Found (%):
C, 41.43; H, 8.12; N, 32.20. C12H28N8O4. Calculated (%):
C, 41.38; H, 8.05; N, 32.18. Structure of compound 3 was conꢀ
firmed by Xꢀray diffraction2 (CCDC 801422).
(t, 8 H, 4 CH2O, 3J = 6.7 Hz); 4.89 (dq, 2 H, 2 CH, 33JСН—СН
=
=
3
1,10ꢀBis(4,5ꢀdimethoxycarbonyltriazolꢀ2ꢀylmethyl)ꢀ1,10ꢀdiꢀ
azaꢀ18ꢀcrownꢀ6 (4). To a solution of 1,10ꢀbis(azidomethyl)ꢀ1,10ꢀ
diazaꢀ18ꢀcrownꢀ6 (2) (0.085 g, 0.228 mmol) in anhydrous MeOH
(2 mL), DMAD (0.065 g, 0.46 mmol) was slowly added. The
reaction mixture was kept for 12 h at room temperature, then
solvent was removed in vacuo, the crystalline residue was recrysꢀ
tallized from methanol—diethyl ether (1 : 1) to give compound 4
in the yield of 0.14 g (93%), m.p. 132—134 C. 1H NMR
(CDCl3), : 3.46 (t, 8 H, 4 CH2N, 3J = 6.1 Hz); 3.57 (s, 8 H,
= 6.7 Hz, 3JCH—NH = 6.7 Hz); 6.26 (d, 2 H, NHCH, 3JNH—CH
= 6.7 Hz); 7.3 (m, 10 H, Ph). Found (%): C, 64.69; H, 7.97;
N, 10.14. C30H44N4O6. Calculated (%): C, 64.75; H, 7.91;
N, 10.07.
References
1. O. G. Nabiev, Z. O. Nabizade, R. G. Kostyanovsky, Menꢀ
deleev Commun., 2009, 19, 281.
3
O(CH2)2O); 3.64 (t, 8 H, 4 CH2O, J = 6.1 Hz); 3.92 (s, 12 H,
2. I. S. Bushmarinov, O. G. Nabiev, R. G. Kostyanovsky,
M. Yu. Antipin, K. A. Lyssenko, CrystEngComm, 2011,
13, 2930.
4 CH3O); 4.64 (c, 4 H, 2 NCH2N). Found (%): C, 47.60; H, 6.15;
N, 17.22. C26H40N8O12. Calculated (%): C, 47.56; H, 6.10;
N, 17.07.
1,10ꢀBis(ꢀphenylethylcarbamoyl)ꢀ1,10ꢀdiazaꢀ18ꢀcrownꢀ6
(6). To a solution of compound 5 (0.8 g, 3 mmol) in anhydrous
MeCN (3 mL), Rꢀ(+)ꢀꢀphenylethyl isocyanate (0.9 g, 6 mmol)
Received June 9, 2013;
in revised form December 23, 2013