Binuclear and polynuclear transition metal complexes with macrocyclic ligands: 7. * Directed step-by-step synthesis of novel unsymmetric macrocyclic ligands

Article abstract of DOI:10.1007/s11172-006-0100-y

Novel asymmetric macrocyclic Schiff bases were synthesized by the condensation of N,N′-bis(2-aminophenyl)-3,4-diphenylthiophene-2,5- dicarboxamide (1) with diformyl derivatives of phenol, furan, difurans, pyridine, pyrrole, and dipyrroles. The reaction pr

Full text of DOI:10.1007/s11172-006-0100-y

Russian Chemical Bulletin, International Edition, Vol. 54, No. 9, pp. 2219—2223, September, 2005
2219
Binuclear and polynuclear transition metal complexes
with macrocyclic ligands
7
.* Directed stepꢀbyꢀstep synthesis of novel unsymmetric macrocyclic ligands**
a
aꢀ
a
b
a
V. V. Roznyatovsky, N. E. Borisova, M. D. Reshetova, A. G. Buyanovskaya, and Yu. A. Ustynyuk
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (095) 939 2677. Eꢀmail: ustynyuk@nmr.chem.msu.su
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
b
2
8 ul. Vavilova, 119991 Moscow, Russian Federation
Novel asymmetric macrocyclic Schiff bases were synthesized by the condensation of
N,N´ꢀbis(2ꢀaminophenyl)ꢀ3,4ꢀdiphenylthiopheneꢀ2,5ꢀdicarboxamide (1) with diformyl deꢀ
rivatives of phenol, furan, difurans, pyridine, pyrrole, and dipyrroles. The reaction proceeds in
high yields and without byꢀproducts in methanol in the presence of inorganic and organic acids
(
protonꢀtemplate condensation). In the case of monocyclic diformyl derivatives and
di(5ꢀformylfuranꢀ2ꢀyl) sulfide, the reaction occurs in 1,4ꢀdioxane (templateless synthesis).
The synthesized macrocycles were characterized by elemental analysis data and NMR and
mass spectra.
Key words: macrocyclic ligands, Schiff bases, stepꢀbyꢀstep synthesis.
Unsymmetric polydentate macrocyclic and acyclic
Scheme 1
Schiff bases and related hybrid systems with donor cenꢀ
ters different in nature are of great interest as ligands for
syntheses of monoꢀ and polynuclear transition metal comꢀ
plexes,2 lanthanides or actinides, and as artificial reꢀ
,3
4,5
6
,7
ceptors for selective anion binding. The modern apꢀ
proaches to the preparation of such systems are mainly
based on stepꢀbyꢀstep syntheses from enlarged precursor
8
blocks (Scheme 1).
The Schiff condensation with macrocycle closure is
8
usually template. Metal ions or anions of protic acids
(
protonꢀtemplate condensation) can be used as template
agents. The latter was proposed for the first time by the
9
Sessler research group and used for the synthesis of sevꢀ
6
,10
eral pyrroleꢀcontaining macrocycles.
Continuing the series of studies on the synthesis of
symmetric and unsymmetric macrocycles based on diꢀ
amines and dicarbonyl compounds, we prepared comꢀ
pound 1, which simultaneously contains groups capable of
binding both anionic and cationic substrates (Scheme 2).
The reactions of diamine 1 with dicarbonyl compounds
of different structure in 1,4ꢀdioxane occur readily already
at room temperature and afford the corresponding macroꢀ
cycles 3—7 in rather high yields and without admixtures
of oligomeric products (Scheme 3).
Dimethylbis(5ꢀformylpyrrolꢀ2ꢀyl)methane, 5,5´ꢀdiꢀ
formylꢀ3,3´ꢀdimethylꢀ4,4´ꢀdipropylꢀ2,2´ꢀdipyrrole, and
5
,5´ꢀdiformylꢀ2,2´ꢀdifuran react with compound 1 less
easily. The reactions do not occur at room temperature,
and only trace amounts of the macrocycles are formed
upon prolong reflux. However, the reaction in methanol
in the presence of protic acids occurs at room temperaꢀ
ture to give macrocycles 8—10 in high yields. Macrocycles
3
—6 can also be obtained by this method in rather high
yields, while macrocycle 7 is not formed under these conꢀ
ditions. The reactions in the presence of protic acids are
performed, depending on the nature of the starting
*
*
For Part 6, see Ref. 1.
* Dedicated to Academician N. S. Zefirov on the occasion of
his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2152—2156, September, 2005.
066ꢀ5285/05/5409ꢀ2219 © 2005 Springer Science+Business Media, Inc.
1

2220
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Roznyatovsky et al.
Scheme 2
Scheme 4
Reaction conditions: i. (for 4—6, 10) HA (conc.), MeOH;
ii. (for 3, 8, 9) 1) HA (conc.), MeOH, 2) Et N, CH Cl .
3
2
2
HA is protic acid.
Comꢀ
HA
Yield
Comꢀ
HA
Yield
pound
(%)
pound
(%)
3
4
5
6
HCl
HCl
HCl
HCl
88
73
73
42
8
9
10
H SO
HCl
95
83
85
70
2
4
H PO
3
4
Scheme 3
CF CO H
3
2
Experimental
NMR spectra were recorded on an AVANCEꢀ400 instruꢀ
1
13
ment (400 MHz for H and 100 MHz for C) at 24 °С. Mass
spectra MALDIꢀTOF were obtained on a Reflex 3 instrument
Bruker) in the positive ion mode. Mass spectra ESI(+) (electroꢀ
spray ionization) were recorded on a FiniganꢀMAT LCQ instruꢀ
ment. Highꢀresolution mass spectra (HRMS) were measured on
a VG ZABꢀ3E instrument with chemical ionization (CI). 2,6ꢀDiꢀ
(
1
1
12
13
formylpyridine, 2,5ꢀdiformylfuran, and 2,5ꢀdiformylpyrrole
were synthesized and purified according to published proceꢀ
1
4
dures. 5,5´ꢀDiformylꢀ2,2´ꢀdifuran, dimethylbis(5ꢀformylꢀ
pyrrolꢀ2ꢀyl)methane, and di(5ꢀformylfuranꢀ2ꢀyl) sulfide16 were
prepared and purified according to described procedures.
,5´ꢀDiformylꢀ3,3´ꢀdimethylꢀ4,4´ꢀdipropylꢀ2,2´ꢀdipyrrole was
15
5
1
7
synthesized similarly. Thiazolidineꢀ2ꢀthione (Acros) was used
without additional purification.
Comꢀ
pound
3
4
5
6
7
3
,4ꢀDiphenylꢀ2,5ꢀbis(2ꢀthioxoꢀ1,3ꢀthiazolidinꢀ3ꢀylcarboꢀ
nyl)thiophene (2). Freshly distilled thionyl chloride (35 mL) and
several droplets of dimethylformamide were added to 3,4ꢀdiꢀ
Yield (%)
80
60
78
85
83
1
8
phenylthiopheneꢀ2,5ꢀdicarboxylic acid (9.0 g, 27.7 mmol).
After reflux for 1 h, the solvent was distilled off under reduced
pressure, and the resulting oily dichloride was dried in vacuo
using a roughing pump at 100 °С. The obtained crystalline subꢀ
stance was dissolved in anhydrous THF (130 mL), and the soluꢀ
tion was added dropwise with stirring at 50 °С for 2 h to a
solution of thiazolidineꢀ2ꢀthione (6.6 g, 55.4 mmol) and triꢀ
ethylamine (20 mL) in anhydrous THF (330 mL). The reaction
mixture was stirred for 2 h at 50 °С and for 16 h at room
temperature, and a precipitate was filtered off and washed with
dicarbonyl compounds and acid, to form either free ligands
—6 and 10 or protonated macrocycles. In the last case,
free ligands 3, 8, and 9 can easily be isolated by the treatꢀ
ment with triethylamine (Scheme 4).
Thus, in this work we obtained the series of novel
macrocyclic Schiff bases. Presently, we are studying their
properties concerning the ability to form complexes with
metal ions and bind anions.
4

Synthesis of asymmetric macrocyclic ligands
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2221
Table 1. Physicochemical characteristics of compounds 3—10
55.80, 127.90, 127.99, 129.60, 134.21, 136.08, 144.34, 164.16,
+
2
00.37. Mass spectrum (ESI+), m/z: 548.9 [M + Na] , 1074.3
+
+
[
2 M + Na] , 1601.8 [3 M + Na] .
Comꢀ M.p.
Found
Molecular
formula
(
%)
N
N,N´ꢀBis(2ꢀaminophenyl)ꢀ3,4ꢀdiphenylthiopheneꢀ2,5ꢀdiꢀ
carboxamide (1). Compound 2 (5.0 g, 9.45 mmol) was added
with stirring to a solution of 1,2ꢀdiaminobenzene (3.1 g,
pound /°C
Calculated
C
H
2
8.4 mmol) in anhydrous CH Cl (125 mL). The reaction mixꢀ
2 2
3
4
5
6
7
8
9
1
>350
>350
74.78
5.08
5.08
4.21 11.71
4.26 11.84
4.08
4.08
4.57 10.74
4.51 10.87
3.82
4.11
5.16 11.37
5.33 11.10
5.61 10.37
5.63 10.43
8.28
8.30
C42H34N O S
4 3
ture was stirred for 2 days at ~20 °C. The precipitate was filtered
off, and compound 1 was obtained in 78% yield (3.7 g), m.p.
2
7
4.76
73.08
3.08
72.87
2.96
72.61
2.32
68.30
C36H25N O S
5 2
28—230 °С (МеСN). Found (%): С, 71.40; Н, 4.77; N, 11.45.
7
C H N O S. Calculated (%): С, 71.41; Н, 4.79; N, 11.10.
3
0
24
4
2
>350
9.43
9.45
C36H24N O S
4 3
1
Н NMR (DMSOꢀd ), δ: 4.50 (s, 4 H, NH ); 6.53 (t, 2 H,
6
2
7
Harom, J = 7.0 Hz); 6.68 (d, 2 H, Harom, J = 7.0 Hz); 6.90 (t,
H, Harom, J = 7.0 Hz); 7.02 (d, 2 H, Harom, J = 7.0 Hz); 7.17
m, 4 H, Harom); 7.25 (m, 6 H, Harom); 8.76 (s, 2 H, CH=N).
>350
C37H25N O S•
5 2
2
(
13
b
7
•0.5С Н О
4 8 2
234—236
decomp.) 68.65
180—182
7.68
7.62
C H N O S •
40 26 4 4 2
С NMR (DMSOꢀd ), δ: 127.48, 127.90, 133.71, 136.90,
b
6
(
•0.5С Н О
4 8 2
1
1
38.13, 139.58, 139.37, 141.32, 145.59, 147.12, 153.39, 153.48,
a
72.93
2.99
71.29
C H N O S•
43 34 6 2
+
71.99. Mass spectrum (ESI+), m/z: 527.1 [M + Na] , 1030.9
c
7
•С Н О
3 6
+
+
[
2 M + Na] , 1535.8 [3 M + Na] .
244—246
C H N O S•
48
44
6
2
1
4ꢀtertꢀButylꢀ31ꢀhydroxyꢀ2,26ꢀdioxoꢀ28,29ꢀdiphenylꢀ3,10,
(
decomp.) 71.58
>350 72.91
2.93
•HCl
C40H26N O S
1
2,16 4,9 19,24
1
8,25ꢀtetraazaꢀ30ꢀthiapentacyclo[25,2,1,1
,0 ,0
]henꢀ
0
4.04
3.98
8.53
8.51
4
4
triacontaꢀ5,7,9(4),10,12(31),13,15,17,19,21,23,27,29ꢀtridecaꢀ
ene (3), 27,28ꢀdiphenylꢀ2,25ꢀdioxaꢀ3,10,17,24,30ꢀpentaazaꢀ29ꢀ
thiapentacyclo[24,2,1,1
12,14,16,18,20,22,26,28ꢀdodecaene (4), 2,25ꢀdioxoꢀ27,28ꢀ
diphenylꢀ3,10,17,24ꢀtetraazaꢀ30ꢀoxaꢀ29ꢀthiapentaꢀ
7
1
2,15 4,9 18,23
a
b
с
,0 ,0
]triacontaꢀ5,7,9(4),10,
For C H N O S •C H O.
4
0
26
4
4
2
3
6
C H O is dioxane.
4
8
2
C H O is acetone.
3
6
1
2,15 4,9 18,23
cyclo[24,2,1,1
6,18,20,22,26,28ꢀdodecaene (5), 2,26ꢀdioxoꢀ28,29ꢀdiꢀ
p h e n y l ꢀ 3 , 1 0 , 1 8 , 2 5 , 3 1 ꢀ p e n t a a z a ꢀ 3 0 ꢀ t h i a p e n t a c y ꢀ
,0 ,0
]triacontaꢀ5,7,9(4),10,12,14,
1
THF (2×30 mL). Combined filtrates were concentrated to dryꢀ
ness on a rotary evaporator. The residue was mixed with ethyl
acetate (30 mL), and a yellow powder (10.8 g, 74%) was filtered
off, m.p. 254—256 °С (from 1,2ꢀdichloroethane). Found (%):
С, 54.73; Н, 3.44; N, 5.32. C H N O S . Calculated (%):
С, 54.98; Н, 3.23; N, 5.36. Н NMR (СDCl ), δ: 2.72 (t, 4 Н,
CH S, J = 7 Hz); 4.21 (t, 4 Н, CH N, J = 7 Hz); 7.05 (m, 4 Н,
Harom); 7.22 (m, 6 Н, Harom). С NMR (СDCl ), δ: 29.61,
1
2,16 4,9 19,24
clo[25,2,1,1
,0 ,0
]hentriacontaꢀ5,7,9(4),10,12(31),
13,15,17,19,21,23,27,29ꢀtridecaene (6), and 2,30ꢀdioxoꢀ32,33ꢀ
diphenylꢀ3,10,22,29ꢀtetrazaꢀ35,36ꢀdioxaꢀ16,34ꢀdithiahexaꢀ
cyclo[29,2,1,1
12,14,17,19,21,23,25,27,31,33ꢀtetradecaene (7) (general proꢀ
cedure). A mixture of diamide 1 (204 mg, 0.4 mmol) and the
corresponding diformyl derivative (0.4 mmol) in a minimum
1
2,15 17,20 4,9 23,28
,1
,0 ,0
]hexatriacontaꢀ5,7,9(4),10,
2
4
18
2
2 5
1
3
2
2
1
3
3
Table 2. Spectral characteristics of compounds 3—10
Comꢀ MALDIꢀTOF
poꢀ mass
und spectrum, m/z
1H NMR, δ, J/Hz*
13C NMR, δ*
t
t
3
675.09
1.39 (s, 9 H, Bu ); 7.14—7.29 (m, 16 H, Harom);
31.51 (3 CH ), 33.88 (C—Bu ), 66.77, 117.12, 120.45,
3
[
[
M + Н]+
7.69 (d, 2 H, Harom, J = 8); 7.99 (s, 2 H, Harom);
.22 (d, 2 H, Harom, J = 8); 9.16 (s, 2 H, CH=N);
0.39 (s, 2 H, NH); 14.42 (br.s, 1 H, OH)
6.94 (d, 2 H, Harom, J = 2); 7.13—7.22 (m, 14 H,
Harom); 7.63 (d, 2 H, Harom, J = 8); 8.25 (d, 2 H,
Harom, J = 8); 8.80 (s, 2 H, CH=N);
121.81, 125.00, 127.82, 127.89, 128.13, 130.47,
133.15, 133.76, 134.66, 135.24, 138.11, 141.58,
145.40, 158.96, 159.09 (C=N), 161.43 (C=O)
115.60, 118.53, 118.58, 123.86, 127.06, 127.10,
127.32, 129.84, 132.31, 134.00, 134.05, 134.83,
136.52, 145.22, 147.14 (C=N), 157.92 (C=O)
8
1
4
592.0
M + H]+
1
0.49 (s, 2 H, NH); 11.89 (s, 1 H, NH of pyrrole)
5
6
593.10
7.05—7.24 (m, 16 H, Harom); 7.36 (d, 2 H, Harom
J = 8); 8.50 (d, 2 H, Harom, J = 8); 8.52 (s, 2 H,
CH=N); 10.38 (s, 2 H, NH)
,
114.67, 119.41, 120.56, 123.68, 127.37, 127.54,
129.43, 130.12, 132.25, 134.41, 135.43, 135.82,
142.66, 148.52, 154.21 (C=N), 157.99 (C=O)
124.80, 126.00, 126.10, 127.10, 127.20, 127.70,
127.90, 128.70, 130.20, 131.30, 134.20, 134.30,
143.40, 161.50 (C=N), 192.90 (C=O)
[
[
M + Н]+
602.35
M – Н]–
7.15 (m, 10 H, Harom); 7.22 (d, 2 H, Harom, J = 7);
7.31 (d, 2 H, Harom, J = 7); 7.35 (d, 2 H, Harom
,
J = 7); 7.55 (d, 2 H, Harom, J = 7); 8.18 (m, 3 H,
Harom); 10.05 (s, 2 H, CH=N); 10.19 (s, 2 H, NH)
(
to be continued)

2222
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
Roznyatovsky et al.
Table 2. Spectral characteristics of compounds 3—10
Comꢀ MALDIꢀTOF
poꢀ mass
und spectrum, m/z
1H NMR, δ, J/Hz*
13C NMR, δ*
7
8
9
691.02
7.10 (t, 2 H, Harom, J = 7); 7.20—7.38 (m, 14 H,
Harom); 7.71 (d, 4 H, Harom, J = 7); 8.01 (d, 2 H,
Harom, J = 8); 8.50 (s, 2 H, CH=N);
108.53, 116.418, 119.448, 121.62, 121.93, 124.42,
127.75, 128.02, 128.32, 130.61, 132.90, 133.36,
137.51, 142.67, 146.17, 153.67 (C=N),
159.57 (C=O)
[
[
[
M + Н]+
9
.07 (s, 2 H, NH)
699.17
M + Н]+
1.83 (s, 6 H, CH ); 6.32 (d, 2 H, Harom, J = 4);
29.27 (CH , acetone), 36.10 (2 CH ), 107.96, 118.07,
3 3
3
6.74 (d, 2 H, Harom, J = 4); 6.93 (m, 2 H, Harom);
119.04, 120.86, 125.11, 126.01, 127.89, 129.72,
130.03, 130.94, 134.20, 142.29, 144.30, 144.79,
150.70 (C=N), 159.61 (C=O)
159.55 (C=O), 146.11 (C=N), 145.95, 140.60,
134.45, 133.50, 133.25, 132.52, 130.09, 128.33,
127.74, 127.67, 126.34, 126.22, 124.94, 121.11,
7
.06—7.18 (m, 14 H, Harom); 7.99 (d, 2 H, Harom
J = 8); 8.18 (s, 2 H, CH=N); 8.22 (s, 2 H, NH)
1.05 (t, 6 H, СН CH , J = 7); 1.68 (m, 4 H,
,
769.16
M + Н]+
2
3
СН CH ); 2.10 (s, 6 H, CH ); 2.80 (t, 4 H,
2 3 3
CСН , J = 7); 7.13—7.28 (m, 16 H, Harom);
2
8
8
.10 (d, 2 H, Harom, J = 4); 8.42 (s, 2 H, CH=N);
.85 (s, 2 H, NH)
120.38, 116.26, 26.23 (2 CH ),
24.75 (2 CH CH CH ), 14.07 (2 CH CH ),
2 2 3 2 3
3
1
0.29 (2 CH CH )
2 3
1
0
659.2**
M + Н]+
7.15—7.42 (m, 20 H, Harom); 7.99 (d, 2 H, Harom
J = 8); 8.55 (s, 2 H, CH=N); 9.72 (s, 2 H, NH)
,
112.25, 117.22, 120.25, 123.10, 124.95, 127.05,
127.33, 129.79, 132.59, 133.13, 134.01, 140.36,
[
1
44.48, 147.09, 151.65 (C=N), 159.12 (C=O)
*
Solvents: DMSOꢀd (compounds 3, 4, 7, 10), CDCl (compounds 5, 8, 9), DMSOꢀd —1% HCl in H O (compound 6).
6
3
6
2
*
* Mass spectrum ESI(+).
amount of anhydrous 1,4ꢀdioxane (10—15 mL) was stirred for
6 h at room temperature. A precipitated product was filtered
off. Compounds 3—7 are solid yellow powders well soluble in
the most part of polar aprotic organic solvents. The analytical
and spectral data are presented in Tables 1 and 2, and the yields
are given in Scheme 3.
(0.20 mmol). A transparent solution that formed was passed
through a thin silica gel layer. The solvent was distilled off on a
rotary evaporator, and the substance was dried in vacuo using a
waterꢀjet pump. Compounds 3, 8, and 9 are solid yellow powꢀ
ders well soluble in the most part of polar aprotic organic solꢀ
vents. The analytical and spectral data of the products are preꢀ
sented in Tables 1 and 2, and the yields and protic acids used are
given in Scheme 4.
1
Macrocycles 4—6 and 2,29ꢀdioxoꢀ31,32ꢀdiphenylꢀ
3
, 1 0 , 2 1 , 2 8 ꢀ t e t r a a z a ꢀ 3 4 , 3 5 ꢀ d i o x a ꢀ 3 3 ꢀ t h i a h e x a c y ꢀ
1
2, 15
1 6 , 1 9
4, 9
2 2 , 2 7
clo[29, 2, 1, 1
, 1
, 0 , 0
]pentatriacontaꢀ
5
(
,7,9(4),10,12,14,16,18,20,22,24,26,30,32ꢀtetradecaene (10)
general procedure). An acid (0.25 mmol) was added to a mixꢀ
ture of compound 1 (51 mg, 0.1 mmol) and diformyl derivative
0.1 mmol) in anhydrous methanol (50—100 mL). After stirring
References
(
1. V. V. Roznyatovsky, N. E. Borisova, M. D. Reshetova, Yu. A.
Ustynyuk, G. G. Aleksandrov, I. L. Eremenko, and I. I.
Moiseev, Izv. Akad. Nauk, Ser. Khim., 2004, 1161 [Russ.
Chem. Bull., Int. Ed., 2004, 53, 1208].
2. P. Guerriero, S. Tamburini, and P. A. Vigato, Coord. Chem.
Rev., 1995, 139, 17.
for 16 h at room temperature, the product was filtered off from
the reaction mixture. Compounds 4—6 and 10 are solid yellow
powders well soluble in the most part of polar aprotic organic
solvents. The analytical and spectral data for the products are
presented in Tables 1 and 2, and the yields and used protic acids
are given in Scheme 4.
Macrocycle 3 and 16,16ꢀdimethylꢀ2,30ꢀdioxoꢀ32,33ꢀdiꢀ
p h e n y l ꢀ 3 , 1 0 , 2 2 , 2 9 , 3 5 , 3 6 ꢀ h e x a a z a ꢀ 3 4 ꢀ t h i a h e x a c y ꢀ
clo[29,2,1,11
3. H. Okawa, H. Furutachi, and D. Fenton, Coord. Chem. Rev.,
1998, 174, 51.
4. J. L. Sessler, G. Hemmi, T. D. Mody, T. Murai, A. Burrell,
and S. W. Young, Acc. Chem. Res., 1994, 27, 43.
5. V. Alexander, Chem. Rev., 1995, 95, 273.
6. J. L. Sessler, E. Kataev, G. D. Pantos, and Yu. A. Ustynyuk,
Chem. Commun., 2004, 1276.
7. J. L. Sessler, S. Camiolo, and P. Gale, Coord. Chem. Rev.,
2003, 240, 17.
8. N. E. Borisova, Yu. A. Ustynyuk, M. D. Reshetova, G. G.
Aleksandrov, I. L. Eremenko, and I. I. Moiseev, Izv. Akad.
Nauk, Ser. Khim., 2004, 326 [Russ. Chem. Bull., Int. Ed.,
2004, 53, 340].
2,15
17,20 4,9 23,28
,1
0,12,14,17,19,21,23,25,27,31,33ꢀtetradecaene (8), and
4, 17ꢀdimethylꢀ2, 29ꢀdioxoꢀ31, 32ꢀdiphenylꢀ13, 18ꢀ
,0 ,0
]hexatriacontaꢀ5,7,9(4),
1
1
dipropylꢀ3,10,21,28,34,35ꢀhexaazaꢀ33ꢀthiahexacyꢀ
clo[29, 2, 1, 1 1
,7,9(4),10,12,14,16,18,20,22,24,26,30,32ꢀtetradecaene (9)
general procedure). An acid (0.25 mmol) was added to a mixture
2, 15
, 1
1 6 , 1 9
, 0 , 0
4, 9
2 2 , 2 7
]pentatriacontaꢀ
5
(
of compound 1 (51 mg, 0.1 mmol) and dialdehyde (0.1 mmol) in
anhydrous methanol (50—100 mL). After stirring for 16 h at
room temperature, the precipitated protonated macrocycle was
filtered off from the reaction mixture. A suspension of the salt of
the product in anhydrous CH Cl was treated with triethylamine
9. J. L. Sessler, M. R. Johnson, and V. Lynch, J. Org. Chem.,
1987, 52, 4394.
2
2

Synthesis of asymmetric macrocyclic ligands
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 9, September, 2005
2223
1
1
1
1
1
1
0. J. L. Sessler, H. Maeda, T. Mizuno, V. M. Lynch, and
H. Furuta, J. Am. Chem. Soc. 2002, 124, 13474.
1. N. W. Alcock, R. G. Kingstone, P. Moore, and C. Pierpoint,
J. Chem. Soc., Dalton Trans., 1984, 1937.
16. Metody polucheniya khimicheskikh reaktivov i preparatov
[Methods for Preparation of Chemical Reagents and Materiꢀ
als], Collection of Works, Issue 22, NIITEKhIM, Moscow,
1970 (in Russian).
17. J. L. Sessler and M. C. Hoehner, Synlett, 1994, 211.
18. H. J. Backer and W. Stevens, Recl. Trav. Chim. PaysꢀBas,
1940, 59, 423.
2. G. Drechsler and G. Kopperschlager, J. Prakt. Chem., 1965,
2
7, 258.
3. K. Olsson and P. Pernemalm, Acta Chem. Scand., 1979,
3, 125.
3
4. G. Märkl, Th. Knott, P. Kreimeier, Th. Burgemeister, and
F. Kastner, Tetrahedron, 1996, 52, 11763.
5. J. L. Sessler, J. Porphyrins Phthalocyanines, 2003, No. 7, 97.
Received June 15, 2005;
in revised form July 20, 2005