Construction of macrocyclic structure using conformational properties of secondary and tertiary aromatic amides

Article abstract of DOI:10.1016/j.tetlet.2005.11.084

A large macrocyclic compound with six para-phenylene rings and six amide moieties, which are alternately secondary and tertiary, was synthesized. In a stepwise synthesis, the final cyclization step was successful because a combination of three tertiary am

Full text of DOI:10.1016/j.tetlet.2005.11.084

Tetrahedron
Letters
Tetrahedron Letters 47 (2006) 803–807
Construction of macrocyclic structure using conformational
properties of secondary and tertiary aromatic amides
Hyuma Masu,a Takako Okamoto,b Takako Kato,a Kosuke Katagiri,a
Masahide Tominaga,a Hiroaki Goda,b Hiroaki Takayanagib and Isao Azumayaa,*
aFaculty of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan
bSchool of Pharmaceutical Sciences, Kitasato University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan
Received 17 October 2005; revised 15 November 2005; accepted 17 November 2005
Available online 5 December 2005
Abstract—A large macrocyclic compound with six para-phenylene rings and six amide moieties, which are alternately secondary and
tertiary, was synthesized. In a stepwise synthesis, the final cyclization step was successful because a combination of three tertiary
amides, which prefer a cis conformation, and two linear secondary amides would arrange both amino and carboxyl ends close
to each other, while various sizes of macrocyclic compounds including the target cyclic trimer were generated in one-pot synthesis
where three secondary amide bonds were formed.
Ó 2005 Elsevier Ltd. All rights reserved.
Aromatic amides have been utilized as versatile frag-
ments to construct frameworks that have various func-
tions such as chemical sensing, conformational switching
or biological activities based on molecular recogni-
tion.1–3 Especially, conformational alternation by N-
alkylation of aromatic amides from trans4 to cis5–7 gives
folded structures to such molecules (Fig. 1). In the
course of our study on the stereochemistry of aromatic
amides, we found that a cyclic structure can be easily
constructed using conformational alternation by the
N-alkyl group on the amide nitrogen. For example,
4- or 3-methylaminobenzoic acid coupled with them-
selves by a one-pot reaction using tetrachlorosilane8,9
or dichlorotriphenylphosphorane10 effectively gives cyc-
lized aromatic amides. On the other hand, the secondary
amide moiety makes a molecule having an extended
structure, which would enlarge the cyclic structure when
the secondary amide is inserted into the cyclic aromatic
amide. Furthermore, the secondary amide moiety,
which can form a hydrogen bonding, would provide a
cavity that interacts with various ligands to the macro-
cyclic compounds. We report the synthesis of a large
cyclic aromatic amide that has secondary and tertiary
amides alternately.
Initially, we designed macrocyclic aromatic amide 3 with
methyl groups for R (Scheme 1) and tried one-pot macro-
cyclization from aromatic amino acid 1 using dichloro-
triphenylphosphorane in 1,1,2,2-tetrachloroethane at
120 °C.10,11 White powder which showed the expected
molecular weight (757: [M+H]+) was obtained (60%
yield) but was hardly soluble in various polar or non-
polar solvents. Next, another aromatic amino acid 2
having a hydrophobic n-decyl group was prepared
and coupled under the same conditions. The resulting
mixture showed 1157, 1536, 1914, 2292, 2670, 3050
([M+Na]+: 3–8mer of 2, respectively) in FAB Mass
spectrum, but complete isolation was difficult because
of the presence of the isomers and many side products.
Figure 1. Conformational alternation by N-alkylation of aromatic
amides.
Keywords: Cyclization; Secondary amide; Tertiary amide; Aromatic
amide; Cyclic amide.
*
Corresponding author. Tel.: +81 87 894 5111; fax: +81 87 894
0181; e-mail: azumayai@kph.bunri-u.ac.jp
0040-4039/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2005.11.084

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H. Masu et al. / Tetrahedron Letters 47 (2006) 803–807
was achieved using 0.5 equiv of iododecane12 because
unreacted and didecylated amine could be easily sepa-
rated by standard silica gel column chromatography
(eluent: ethyl acetate–hexane = 1:6). After 4-nitrobenzo-
ylation, compound 7 was converted to amine 8 by
hydrogenation over Pd/C, and to carboxylic acid 9 by
hydrolysis. A key amidation reaction of 8 and 9 was suc-
cessful by using dichlorotriphenylphosphorane in high
yield (73%). Oligomer 10 was hydrolyzed, followed by
amidation with 8 by dichlorotriphenylphosphorane to
give oligomer 12. Reduction of the nitro group followed
by hydrolysis gave the chained aromatic amino acid 14
having six phenylene groups.
The final cyclization reaction (0.03 M of 14) was also
achieved using dichlorotriphenylphosphorane to give
the target macrocyclic aromatic amide 4.15 The yield
was lower than expected (16%), but a compound having
a double mass number (6mer)16 was obtained in lower
yield (12%) and a complex of more polymerized com-
pounds was obtained (23% yield). A possible reason
Scheme 1. One-pot macrocyclization from aromatic amino acid.
So we synthesized the macrocyclic compounds 4 from
ethyl 4-aminobenzoate 5 stepwise as shown in Scheme
2.14 Direct monoalkylation of an aromatic amino group
Scheme 2. Reagents and conditions: (a) n-C10H21I, HMPA, 120 °C, 2.5 h; (b) 4-nitrobenzoylchloride, pyridine, rt, 1.5 h; (c) 10% Pd/C, H2, EtOH, rt,
2h; (d) 4 N NaOH, EtOH, rt, 45 min; (e) Ph3PCl2, CHCl3, reflux, 3 h; (f) 4 M NaOH, EtOH, rt, 30 min; (g) 8, Ph3PCl2, CHCl3, reflux, 2 h; (h) 10%
Pd/C, H2, EtOH, rt, 14 h; (i) 4 M NaOH, EtOH, rt, 1.5 h; (j) Ph3PCl2, CHCl3, reflux, 8.5 h.

H. Masu et al. / Tetrahedron Letters 47 (2006) 803–807
805
why the yield of the macrocyclized compound was lower
than that in the one-pot cyclization of 4-methylamino-
benzoic acid by dichlorotriphenylphosphorane10 could
be because the oligomeric amino acid 14 right before
the macrocyclization could exist in various conforma-
tion due to phenylene-N or phenylene-CO rotations. A
few conformations out of the many possible conforma-
tions should be preferable to the cyclization, contrary
to that one conformation (the terminal two benzene
rings located in syn conformation) out of two possible
conformations (syn or anti) are preferable in the final
amidation step in the one-pot cyclization of 4-methyl-
aminobenzoic acid.
In conclusion, we achieved a synthesis of a large cyclic
aromatic amide that has secondary and tertiary amides
alternately, by utilizing their conformational properties.
This strategy can produce macrocyclic compounds with
various sizes of cavities. Details of the dynamic behavior
and inclusion properties of the macrocyclic aromatic
amide 4 are now under study.
References and notes
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Sullivian, R. W.; Bigam, C. G.; Erdman, P. E.; Palanki,
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1
In the H NMR spectrum of macrocyclic compound 4,
four slightly broadened doublet aromatic protons were
observed (d 7.04, 7.18, 7.46, 7.73). This shows the
dynamic behavior of 4 has C3h symmetry in the NMR
timescale at room temperature. Three N-decylamide
groups would have adopted cis (E) conformation since
a ROESY correlation was observed between aromatic
protons ortho to the decyl-N and aromatic protons ortho
to the carbonyl of NH-amide, and no ROESY correla-
tion was observed between protons ortho to the NH
and protons ortho to the carbonyl of N-decylamide.
Therefore, macrocyclic compound 4 existed, as expec-
ted, in a conformation with a large triangle (Scheme
1), due to a cis-preference of the tertiary amide and a
trans-preference of the secondary amide.
Preliminary conformational analysis was performed on
ÔSPARTANÕ02 for LinuxÕ program.13 The most promis-
ing structure among AM1-minimized conformations of
macrocyclic compound 3 (after conformational search
using Monte Carlo method on MMFF94 force field) is
shown in Figure 2. This conformation, where all the
amide planes are located in the same direction, is corre-
4. (a) Stewart, W. E.; Siddall, T. H., III. Chem. Rev. 1970, 70,
517–551; (b) Kashino, S.; Ito, K.; Haisa, M. Bull. Chem.
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Acta Chem. Scand. 1967, 21, 1415–1424; (d) Nanjan, M. J.;
Kannappan, V.; Ganesan, R. Indian J. Chem. 1979, 18B,
461–463.
1
sponding to the symmetrical H NMR spectrum of 3
due to local conformational equilibria including twist
of phenylene rings and amide bondings.
6. (a) Itai, A.; Toriumi, Y.; Tomioka, N.; Kagechika, H.;
Azumaya, I.; Shudo, K. Tetrahedron Lett. 1989, 30, 6177–
6180; (b) Azumaya, I.; Kagechika, H.; Fujiwara, Y.; Itoh,
M.; Yamaguchi, K.; Shudo, K. J. Am. Chem. Soc. 1991,
113, 2833–2838; (c) Yamaguchi, K.; Matsumura, G.;
Kagechika, H.; Azumaya, I.; Ito, Y.; Itai, A.; Shudo, K.
J. Am. Chem. Soc. 1991, 113, 5474–5475; (d) Itai, A.;
Toriumi, Y.; Saito, S.; Kagechika, H.; Shudo, K. J. Am.
Chem. Soc. 1992, 114, 10649–10650; (e) Saito, S.; Toriumi,
Y.; Tomioka, N.; Itai, A. J. Org. Chem. 1995, 60, 4715–
4720; (f) Azumaya, I.; Kagechika, H.; Yamaguchi, K.;
Shudo, K. Tetrahedron 1995, 51, 5277–5290; (g) Tanatani,
A.; Yamaguchi, K.; Azumaya, I.; Fukutomi, R.; Shudo,
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6442.
7. (a) Manea, V. P.; Wilson, K. J.; Cable, J. R. J. Am. Chem.
Soc. 1997, 119, 2033–2039; (b) Takeuchi, Y.; Marshall, G.
R. J. Am. Chem. Soc. 1998, 120, 5363–5372; (c) Okubo,
H.; Yamaguchi, M.; Kabuto, C. J. Org. Chem. 1998, 63,
9500–9509.
Figure 2. AM1-optimized structure of macrocyclic amide 3 starting
from the most stable conformation obtained by conformational search
calculation using MMFF94 force field.

806
H. Masu et al. / Tetrahedron Letters 47 (2006) 803–807
8. Azumaya, I.; Kagechika, H.; Yamaguchi, K.; Shudo, K.
27.8, 29.2, 29.3, 29.5, 31.8, 50.5, 50.5, 61.1, 119.0, 123.3,
127.1, 127.8, 128.3, 128.4, 129.5, 130.0, 130.5, 131.9, 133.2,
139.0, 142.0, 145.8, 147.8, 148.1, 164.1, 165.7, 168.0, 169.5.
MS (FAB) m/z = 833 [M+H]+. Anal. Calcd for
C50H64N4O7: C, 72.09; H, 7.74; N, 6.73. Found: C,
71.96; H, 7.79; N, 6.72. Compound 11: Pale yellow
Tetrahedron Lett. 1996, 37, 5003–5006.
9. Azumaya, I.; Okamoto, T.; Takayanagi, H. Anal. Sci.
2001, 17, 1363–1364.
10. Azumaya, I.; Okamoto, T.; Imabeppu, F.; Takayanagi, H.
Tetrahedron 2003, 59, 2325–2331.
11. A monomer that is a structural isomer of 3 was cyclized
using triphenyl phosphite as condensing agent to give a
similar cyclic trimer: Lorenzi, G. P.; Tomasic, L.; Suter, U.
W. Macromolecules 1993, 26, 1183–1185.
1
amorphous. H NMR (400 MHz, CDCl3): d 0.86 (6H, t,
J = 7.0 Hz), 1.18–1.38 (28H, br m), 1.58–1.68 (4H, br m),
3.94 (4H, br t, J = 7.0 Hz), 7.09 (4H, d, J = 9.0 Hz), 7.27
(2H, d, J = 9.0 Hz), 7.42 (4H, dd, J = 9.0, 2.0 Hz), 7.72
(2H, d, J = 9.0 Hz), 7.87 (1H, br s), 7.93 (2H, d,
J = 9.0 Hz), 8.0 (2H, d, J = 9.0 Hz). 13C NMR
(100 MHz, CDCl3): d 14.1, 22.6, 26.8, 26.9, 27.7, 27.8,
29.2, 29.3, 29.5, 31.8, 50.6, 119.0, 123.2, 127.0, 127.2,
127.8, 128.4, 129.5, 130.1, 131.2, 131.7, 133.2, 139.2,
142.0, 145.8, 148.1, 148.6, 164.3, 168.0, 169.6, 169.6. MS
(FAB) m/z = 805 [M+H]+. HRMS (FAB) Calcd for
C48H60N4O7Na [M+Na]+: 827.4360. Found: 827.4360.
Compound 12: Pale yellow amorphous. 1H NMR
(400 MHz, CDCl3): d 0.83–0.89 (9H, m), 1.18–1.38 (42H,
br m), 1.36 (3H, t, J = 7.0 Hz), 1.54–1.65 (6H, br m), 3.86–
3.96 (6H, br m), 4.33 (2H, q, J = 7.0 Hz), 7.07 (4H, d,
J = 8.5 Hz), 7.09 (2H, d, J = 8.5 Hz), 7.23 (2H, d,
J = 8.5 Hz), 7.26 (2H, d, J = 8.5 Hz), 7.36 (2H, d, J =
8.5 Hz), 7.42 (2H, d, J = 8.5 Hz), 7.43 (2H, d, J = 8.5 Hz),
7.68 (2H, d, J = 8.5 Hz), 7.70 (2H, d, J = 8.5 Hz), 7.90
(2H, d, J = 8.5 Hz), 7.96 (1H, br s), 8.03 (2H, d,
J = 8.5 Hz), 8.08 (1H, br s). 13C NMR (100 MHz, CDCl3):
d 14.1, 14.3, 22.6, 26.8, 26.9, 27.8, 27.8, 29.2, 29.3, 29.5,
31.8, 50.6, 50.6, 61.1, 118.9, 119.2, 123.3, 127.1, 127.5,
127.8, 128.2, 128.2, 128.4, 129.4, 129.9, 130.0, 130.5, 131.7,
131.9, 132.4, 133.1, 139.0, 139.3, 142.0, 145.8, 147.0,
147.9, 148.1, 164.4, 164.7, 165.7, 168.0, 169.5. MS
(FAB) m/z = 1211 [M+H]+. HRMS (FAB) Calcd for
C74H94N6O9Na [M+Na]+: 1233.6980. Found: 1233.6962.
Compound 13: Pale yellow amorphous. 1H NMR
(400 MHz, CDCl3): d 0.83–0.90 (9H, m), 1.18–1.38 (42H,
br m), 1.35 (3H, t, J = 7.0 Hz), 1.50–1.64 (6H, br m), 3.80–
3.95 (8H, br m), 4.32 (2H, q, J = 7.0 Hz), 6.38 (2H, d,
J = 8.5 Hz), 7.00 (2H, d, J = 8.5 Hz), 7.02 (2H, d,
J = 8.5 Hz), 7.06 (2H, d, J = 8.5 Hz), 7.09 (2H, d, J =
8.5 Hz), 7.15 (2H, d, J = 8.5 Hz), 7.23 (2H, d, J = 8.5 Hz),
7.31 (2H, d, J = 8.5 Hz), 7.47 (2H, d, J = 8.5 Hz), 7.58
(2H, d, J = 8.5 Hz), 7.74 (2H, d, J = 8.5 Hz), 7.89 (2H, d,
J = 8.5 Hz), 8.28 (1H, br s), 8.69 (1H, br s). 13C NMR
(100 MHz, CDCl3): d 14.1, 14.3, 22.6, 26.9, 26.9, 27.8,
28.1, 29.3, 29.3, 29.3, 29.3, 29.5, 29.5, 29.5, 31.8, 50.5, 50.6,
50.8, 61.1, 113.6, 119.0, 119.4, 123.6, 124.9, 127.1, 127.2,
127.5, 128.0, 128.2, 128.4, 129.7, 129.9, 130.5, 130.9, 131.4,
131.5, 131.7, 132.5, 139.2, 139.7, 146.9, 147.9, 147.9, 148.5,
164.8, 165.4, 165.7, 169.6, 169.7, 170.4. MS (FAB)
m/z = 1181 [M+H]+. HRMS (FAB) Calcd for
C74H96N6O7Na [M+Na]+: 1203.7238. Found 1203.7263.
Compound 14: Pale yellow amorphous. 1H NMR
(400 MHz, CDCl3): d 0.85 (9H, br t, J = 7.0 Hz), 1.12–
1.35 (42H, br m), 1.49 (2H, br s), 1.58 (4H, br s), 3.74 (2H,
br s), 3.89 (4H, br s), 6.42 (2H, br d), 6.88 (2H, br d), 6.94–
7.06 (6H, br m), 7.07–7.16 (4H, br m), 7.30 (2H, br s), 7.43
(4H, br d), 7.80 (2H, br d), 7.90 (2H, br d), 8.84 (1H, br s),
9.60 (1H, br s). 13C NMR (100 MHz, CDCl3): d 14.1, 22.6,
26.8, 26.9, 27.7, 27.8, 28.2, 29.2, 29.2, 29.3, 29.5, 29.5, 31.8,
50.3, 50.7, 51.2, 124.4, 127.0, 127.1, 127.3, 127.6, 128.1,
128.8, 129.4, 129.8, 130.4, 130.8, 130.8, 131.4, 132.3, 132.8,
113.9, 118.7, 119.4, 139.3, 140.2, 146.5, 146.6, 148.3, 148.6,
165.0, 166.1, 168.4, 169.7, 170.2, 171.3. MS (FAB)
m/z = 1175 [M+Na]+. HRMS (FAB) Calcd for
C72H91N6O7Na2 [M+Na2]+: 1197.6745. Found 1197.6788.
15. Spectral data of compound 4: White amorphous. 1H
NMR (400 MHz, CDCl3): d 0.89 (9H, br t), 1.16–1.38
12. Yokozawa, T.; Asai, T.; Sugi, R.; Ishigooka, S.; Hiraoka,
S. J. Am. Chem. Soc. 2000, 122, 8313–8314.
13. SPARTANÕ02 for Linux: Wavefunction, Inc.
14. Spectral data of compound 6–14. Compound 6: White
1
powder, mp 71 °C. H NMR (400 MHz, CDCl3): d 0.88
(3H, t, J = 7.0 Hz), 1.20–1.45 (14H, br m), 1.36 (3H, t,
J = 7.0 Hz), 1.62 (2H, tt, J = 7.0, 7.0 Hz), 3.15 (2H, t,
J = 7.0 Hz), 4.13 (1H, br s), 4.31 (2H, t, J = 7.0 Hz), 6.54
(2H, ddd, J = 9.0, 2.0, 2.0 Hz), 7.86 (2H, ddd, J = 9.0, 2.0,
2.0 Hz). 13C NMR (100 MHz, CDCl3): d 14.1, 14.4, 22.6,
27.0, 29.3, 29.3, 29.4, 29.5, 29.5, 31.9, 43.4, 60.1, 111.3,
118.4, 131.5, 152.0, 166.9. MS (DI-EI) m/z = 305 [M+].
Anal. Calcd for C19H31NO2: C, 74.71; H, 10.23; N, 4.59.
Found: C, 74.47; H, 10.12; N, 4.70. Compound 7: Pale
1
yellow amorphous. H NMR (400 MHz, CDCl3): d 0.87
(3H, t, J = 7.0 Hz), 1.18–1.40 (14H, br m), 1.36 (3H, t,
J = 7.0 Hz), 1.61 (2H, tt, J = 7.0, 7.0 Hz), 3.95 (2H,
t, J = 7.0 Hz), 4.34 (2H, q, J = 7.0 Hz), 7.06 (2H, ddd,
J = 9.0, 2.0, 2.0 Hz), 7.43 (2H, ddd, J = 9.0, 2.0, 2.0 Hz),
7.92 (2H, ddd, J = 9.0, 2.0, 2.0 Hz), 8.03 (2H, ddd,
J = 9.0, 2.0, 2.0 Hz). 13C NMR (100 MHz, CDCl3): d
14.1, 14.2, 22.6, 26.8, 27.7, 29.2, 29.5, 31.8, 50.4, 61.3,
142.1, 146.5, 148.1, 123.2, 127.4, 129.2, 129.5, 130.8, 165.4,
168.0. MS (DI-EI) m/z = 454 [M+]. Anal. Calcd for
C26H34N2O5: C, 68.70; H, 7.54; N, 6.16. Found: C,
68.62; H, 7.61; N, 6.29. Compound 8: White powder,
mp 56 °C. 1H NMR (400 MHz, CDCl3): d 0.86 (3H,
t, J = 7.0 Hz), 1.18–1.40 (14H, br m), 1.36 (3H, t,
J = 7.0 Hz), 1.56–1.66 (2H, br m), 3.79 (2H, br s), 3.90
(2H, t, J = 7.0 Hz), 4.34 (2H, q, J = 7.0 Hz), 6.40 (2H,
ddd, J = 9.0, 2.0, 2.0 Hz), 7.06 (2H, ddd, J = 9.0, 2.0,
2.0 Hz), 7.11 (2H, ddd, J = 9.0, 2.0, 9.0 Hz), 7.89 (2H,
ddd, J = 9.0, 2.0, 2.0 Hz). 13C NMR (100 MHz, CDCl3): d
14.1, 14.3, 22.6, 27.0, 27.9, 29.2, 29.3, 29.5, 29.5, 31.8, 50.6,
61.0, 113.6, 123.6, 126.8, 127.5, 130.4, 131.1, 148.2, 148.8,
165.9, 170.2. MS (FAB) m/z = 425 [M+H]+. Anal. Calcd
for C26H36N2O3: C, 73.55; H, 8.55; N, 6.60. Found: C,
73.41; H, 8.54; N, 6.73. Compound 9: White powder, mp
108 °C. 1H NMR (400 MHz, CDCl3): d 0.87 (3H, t,
J = 7.0 Hz), 1.18–1.40 (14H, br m), 1.57–1.68 (2H, br m),
3.97 (2H, t, J = 7.0 Hz), 7.11 (2H, ddd, J = 9.0, 2.0,
2.0 Hz), 7.44 (2H, ddd, J = 9.0, 2.0, 2.0 Hz), 7.97 (2H,
ddd, J = 9.0, 2.0, 2.0 Hz), 8.04 (2H, ddd, J = 9.0, 2.0,
2.0 Hz). 13C NMR (100 MHz, CDCl3): d 14.1, 22.6, 26.8,
27.7, 29.2, 29.5, 31.8, 50.5, 123.3, 127.4, 127.9, 129.5,
131.5, 141.8, 147.4, 148.2, 168.1, 170.2. MS (DI-EI)
m/z = 426 [M+]. Anal. Calcd for C24H30N2O5: C, 67.59;
H, 7.09; N, 6.57. Found: C, 67.30; H, 6.90; N, 6.67.
1
Compound 10: Yellow amorphous. H NMR (400 MHz,
CDCl3): d 0.86 (6H, t, J = 7.0 Hz), 1.18–1.40 (28H, br m),
1.36 (3H, t, J = 7.0 Hz), 1.55–1.65 (4H, br m), 3.92 (2H, t,
J = 7.0 Hz), 3.94 (2H, t, J = 7.0 Hz), 4.33 (2H, q,
J = 7.0 Hz), 7.06 (2H, ddd, J = 9.0, 2.0, 2.0 Hz), 7.10
(2H, ddd, J = 9.0, 2.0, 2.0 Hz), 7.26 (2H, ddd, J = 9.0, 2.0,
2.0 Hz), 7.41 (2H, ddd, J = 9.0, 2.0, 2.0 Hz), 7.43 (2H,
ddd, J = 9.0, 2.0, 2.0 Hz), 7.72 (2H, ddd, J = 9.0, 2.0,
2.0 Hz), 7.81 (1H, br s), 7.89 (2H, ddd, J = 9.0, 2.0,
2.0 Hz), 8.03 (2H, ddd, J = 9.0, 2.0, 2.0 Hz). 13C NMR
(100 MHz, CDCl3): d 14.1, 14.3, 22.6, 26.8, 26.9, 27.7,

H. Masu et al. / Tetrahedron Letters 47 (2006) 803–807
807
(42H, br m), 1.54–1.70 (6H, br m), 3.89–3.99 (6H, br t),
7.04 (6H, br d, J = 8.0 Hz), 7.18 (6H, br d, J = 8.0 Hz),
7.46 (6H, br d, J = 8.0 Hz), 7.73 (6H, br d, J = 8.0 Hz),
8.07 (3H, br s). 13C NMR (100 MHz, CDCl3): d 14.1,
22.7, 27.0, 27.9, 29.3, 29.3, 29.5, 29.5, 31.9, 50.1, 118.8,
127.7, 128.1, 129.8, 131.6, 131.8, 139.1, 147.5, 164.1,
169.9. MS (FAB) m/z = 1135 [M+H]+. HRMS (FAB)
Calcd for C72H91N6O6 [M+H]+: 1135.7000. Found
1135.6979.
16. Spectral data of dimer of compound 4: White amorphous.
1H NMR (400 MHz, CDCl3): d 0.89 (18H, br t), 1.24–1.67
(99H, m), 3.71 (3H, m), 3.93 (3H, m), 4.20 (3H, m), 5.60
(2H, d, J = 8.8 Hz), 6.32 (2H, d, J = 8.8 Hz), 6.81 (2H, d,
J = 8.4 Hz), 7.06 (2H, d, J = 9.2 Hz), 7.14 (2H, d,
J = 8.8 Hz), 7.22 (2H, d, J = 8.4 Hz), 7.29 (31H, m),
7.43 (2H, d, J = 7.2 Hz), 7.60 (2H, d, J = 8.4 Hz), 7.66
(2H, m), 8.06 (2H, d, J = 8.4 Hz), 8.11 (1H, br), 8.70–8.79
(2H, m). MS (ESI) m/z = 2270 [M+H]+.