Synthesis and characterization of new polyoxa-aza cryptands

Article abstract of DOI:10.1081/SCC-120013721

In this paper, two new polyoxa-aza cryptands were synthesized in high yield (70-80%) and characterized with elemental analyses, ¹H NMR, ¹³C NMR, IR, and MS methods.

Full text of DOI:10.1081/SCC-120013721

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SYNTHESIS AND CHARACTERIZATION OF NEW POLYOXA-
AZA CRYPTANDS
Jianjun Yu a & Rudong Yang b
a College of Chemistry and Chemical Engineering, Lanzhou University, Gansu, 730000, China
b College of Chemistry and Chemical Engineering, Lanzhou University, Gansu, 730000, China
Version of record first published: 16 Aug 2006.
To cite this article: Jianjun Yu & Rudong Yang (2002): SYNTHESIS AND CHARACTERIZATION OF NEW POLYOXA-AZA CRYPTANDS,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:20,
3113-3117
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 20, pp. 3113–3117, 2002
SYNTHESIS AND CHARACTERIZATION
OF NEW POLYOXA-AZA CRYPTANDS
*
Jianjun Yu and Rudong Yang
College of Chemistry and Chemical Engineering,
Lanzhou University, Gansu, 730000, China
ABSTRACT
In this paper, two new polyoxa-aza cryptands were synthe-
sized in high yield (70–80%) and characterized with elemental
1
analyses, H NMR, 13C NMR, IR, and MS methods.
Macropolycyclic ligands have distinctive structures and properties,
they as synthetic receptors for organic or inorganic cations, anions or
neutral molecules play important roles in a number of areas in chemistry
and biochemistry.[1–3] Thus they have potential applications in exploring new
materials, analysis and separation of the rare earth ions, supramolecular
devices, luminescent labels, fluorescent probes, magnetic resonance imaging
and catalytic cleavage of RNA. In order to study the interaction between
macropolycyclic ligands and rare earth ions, the present set of macrobicyclic
cryptands were designed to include two and over metal ions inside the
cavity, which is the area of considerable current interest. Macrobicyclic
cryptands have not been used as extensively as the macrocyclic cryptands,
*Corresponding author. E-mail: yuwangs@public.lz.gs.cn
3113
DOI: 10.1081/SCC-120013721
Copyright & 2002 by Marcel Dekker, Inc.
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3114YU AND YANG
owing in part to difficulties associated with their synthesis.[4] The usual
method of synthesis of these molecules involves linking of macrocycles
through their functionalizable sites with spacers to delineate the central
cavity of the compound. However, the method of synthesis starting from
acyclic precursors, usually affords the desired cryptand in lowyields. In this
thesis, two polyoxa-aza cryptands (L1 and L2) were synthesized in high yield
by [1 þ 1] or [2 þ 3] cyclocondensation and hydrogenation, where rare earth
elements act as template. Synthesis process of the products were shown in
Schs. 1 and 2.
DMF was the traditional solvent in the synthesis of compound 1.
However, methanol and ethanol were chosen for our synthesis process,
because the higher yields (>90%) than those reactions in DMF were
gotten.[5]
Scheme 1.
Scheme 2.

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NEW POLYOXA-AZA CRYPTANDS
3115
The conditions is as follows in the synthesis of cryptands L1: To avoid
collision of reactants, (1) The temperature should be the room temperature
and not over 25ꢀC; (2) 2 should be dropped into the systems to keep a low
concentration of reactants. And, for reactions between two compounds
having three opening bond respectively, templating metal ions is very
important to make them near and react with each other. For the easier
removal of rare earth ion at the end of reactions, rare earth ion were usually
chosen for templating metal ion, instead of base metal. No water appeared
in reactions, otherwise rare earth ion would undergo hydrolysis.
Since linear diamine release the cyclic strain, templating ion is not
necessary in the synthesis of cryptands L2. Yield of L2 is lower than that
of L1, probably because the reaction took place in three different molecules,
which led to more by-products.
In summary, we reported the facile synthesis of two new macrobicyclic
cryptands (Schs. 1 and 2) in high yields. They are both stable. Currently,
studies in function of the cryptands are in progress, especially in their
electrochemical and fluorescent characteristics. The studies for their
recognition characteristics towards neutral molecules, anions and cations
are also in progress. The results will be reported later.
EXPERIMENTAL
Elemental analyses were determined with the Elementar Vario EL
elemental analyzers. The IR spectra were obtained on the Nicolet FT-170
SX model FT-IR spectrophotometer, using KBr pellets. Melting point were
measured with the X4 microscopic melting point apparatus by Beijing third
Optical Instrument Factory and the thermometer used in determination
1
process was not calibrated. H NMR spectra were measured with Bruker
AC-80 NMR and 13C NMR spectra were obtained with Bruker AM-200
NMR. The FAB-MS date were obtained with the VG 2BA-HS model MS.
The rare earth oxide were bought from Shanghai Yuelong Chemical
Factory and were at least of 99.99% purity. Rare earth (III) nitrates were
prepared according to the literature method.[6]
3-Methoxy-4-hydroxybenzaldehyde (A.P) and triethanolamine (A.R.)
were purchased from Shanghai Chemical Reagent third Factory.
Other reagents used in experiments were all purified as need.[7]
Tri{[2-(29-methoxy-49-oxomethyl-phenyl)-oxy]-ethyl}amine 1: 3-Methoxy-
4-hydroxybenzaldehyde (4.56 g, 30 mmol) and tris(2-chloroethyl)amine
hydrochloride (2.41 g, 10 mmol) and anhydrous potassium carbonate were
dissolved in 100 mL ethanol and stirred for 12 h at reflux. Then 100 mL of
water added. The yellow precipitate was formed immediately, filtered off,

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3116
YU AND YANG
recrystallized twice with ethanol, dried under reduced pressure and a white
crystal was obtained (95% yield), m.p. 82–84ꢀC. IR spectrum gave a strong
band of vC¼O at 1713 cmꢁ1. Satisfactory elemental analysis of C, 65.34; H,
5.99; N, 2.50 were obtained (C30H33O9N requires C, 65.34; H, 5.99; N, 2.54).
1H NMR (80 MHz, CDCl3) dH: 3.3 (t, J ¼ 6.0 Hz, 6H, NCH2), 3.9
(s, 9H, OCH3), 4.3 (t, J ¼ 6.0 Hz, 6H, OCH2), 6.8–7.4 (m, 9H, aromatic),
9.7 (s, 3H, CHO).
Synthesis of Tris(2-aminoethyl)amine 2: synthesized as methods in
literature.[8]
Synthesis of cryptand (L1): tris(2-Aminoethyl)amine (1.0 mmol,
0.146 g) in 50 mL of absolute methanol was added dropwise into 100 mL
absolute methanol, in which 1 (1.0 mmol, 0.551 g) and rare earth nitrates
(2.0 mmol) were dissolved, within 4 h at ambient temperature. After stirring
for 24 h, the Schiff base was formed and hydrogenated in situ by stirring at
room temperature for 12 h with NaBH4. Then 20 mL of 1 : 1 ammonia sol-
ution was added into the liquor and rare earth ion was precipitated and
filtered off. Finally, the solvent was evaporated to almost dryness and the
residue was shaken with 80 mL of water, the cryptand was extracted from
the aqueous medium with CHCl3 (3 ꢂ 30 mL). The organic layer was dried
over anhydrous Na2SO4 and evaporated completely to obtain the desired
product L1 (70% yield). L1 was a white powder [Found: C, 66.50; H, 8.07;
N, 10.98; C36H51O6N5 requires C, 66.56; H, 7.86; N, 10.79]; 1H NMR
(80 MHz, DMSO) dH: 3.0 (t, J ¼ 5.0 Hz, 6H, a), 3.4 (t, J ¼ 5.0 Hz, 12H, b
and f), 3.7 (s, 9H, d), 4.0 (t, J ¼ 5.0 Hz, 6H, e), 4.4 (s, 6H, c), 5.1 (brs, 3H, -
NH), 6.7–7.0 (m, 12H, benzene); 13C NMR (50 MHz, DMSO) dc: 53.95 (3C,
a), 55.45 (6C, b and f), 62.78 (6C, c and d), 67.47 (3C, e), 110.86 (3C,
benzene), 112.99 (3C, benzene), 118.60 (3C, benzene), 135.28 (3C, benzene),
146.89 (3C, benzene), 148.87 (3C, benzene); FAB-MS m/z: 650 [L1 þ H]þ.
Synthesis of cryptand (L2): The ethylene diamine (3 mmol, 0.18 g) was
dissolved in 20 mL of absolute methanol at room temperature. The solution
was added dropwise into a solution of 1 (1.0 mmol) dissolved in 100 mL
absolute methanol within 6 h at room temperature, then stirred for 24 h.
The yellow Schiff base was formed and hydrogenated with NaBH4 by stirring
for 2 h at 10ꢀC. After the solvent was distilled off under reduced pressure, the
residue was shaken with 50 mL of water and extracted with CHCl3 (3 ꢂ 30).
Then the aqueous medium was removed, the organic layer was dried over
anhydrous Na2SO4 and evaporated. The desired product (L2) was obtained
(68% yield). L2 was a white powder [Found: C, 66.67; H, 7.48; N, 9.63;
C66H90O12N8 requires C, 66.78; H, 7.59; N, 9.44]; 1H NMR (80 MHz,
CDCl3) dH: 1.9 (brs, 12H, NH), 2.9 (m, 12H, –NHCH2–), 3.2 (t, J ¼ 6.0 Hz,
12H, N(CH2)3), 3.8 (s, 18H, OCH3), 3.9 (t, J ¼ 6.0 Hz, 12H, –OCH2–), 4.6
(s, 12H, Ar), 6.7–7.3 (m, 24H, benzene); FAB-MS m/z: 1187 [L2 þ H]þ.

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NEW POLYOXA-AZA CRYPTANDS
ACKNOWLEDGMENT
3117
The National Education Committee’s Doctoral Foundation of China
(9573005) financially supported this work.
REFERENCES
1. Lehn, J.M. Supramolecular Chemistry; VCH: Weinheim, 1995.
2. Ragunathan, K.G.; Bharadwaj, P.K. Tetrahedron Lett. 1992, 33, 7581.
3. Lehn, J.M. Acc. Chem. Res. 1978, 11, 49.
4. Krakowiak, K.E.; Bradshaw, J.S.; Dalley, N.K.; Zhu, C.Y.; Yi, G.L.;
Curtis, J.L.; Li, D.; Izatt, R.M. J. Org. Chem. 1992, 57, 3166.
5. Ma, Z.; Yang, R.D.; Yan, L. Chin. Chem. Lett. 1999, 10, 995.
6. Wendland, W.W. Anal. Chim. Acta 1956, 15, 435.
7. Zhang, G.C.; Tan, Z. Experiment of Fine Organic Chemistry. Publishing
House of Lanzhou University, 2000, pp. 13–30.
8. Kimura, S.; Young, S.; Collman, J.P. Inorg. Chem. 1970, 9, 1183.
Received in Japan July 16, 2001

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