K. Katagiri et al. / Journal of Molecular Structure 891 (2008) 346–350
347
1
1.6 mmol) with stirring at 80 °C. After 2 h, the reaction mixture
was poured into ice and was extracted with AcOEt. The organic
layer was washed with 2 N HCl, sat. NaHCO , brine and dried over
Na SO . The solvent was evaporated and the remaining HMPA in
2.5. Hexamer of 6-allylamino-2-naphthoic acid (6)
3
To a solution of 6-allylamino-2-natphthoic acid (4) (1.22 g,
5.4 mmol) in 1,1,2,2,-tetrachloroethane (54 mL) under Ar was
added dichlorotriphenylphosphorane (4.32 g, 13.0 mmol) with
stirring for 6 h at 120 °C. The solvent was removed under reduced
pressure, and the residue was purified by column chromatography
2
4
the residue was removed azeotropically with toluene under re-
duced pressure. The crude product was purified by silica gel col-
umn chromatography (eluent = CHCl3: toluene: NEt
3
= 1:6:0.025)
to give pure methyl 6-allylamino-2-naphthoate (3) (1.71 g, 61ꢀ):
on silica gel (eluent: CHCl
hexamer. The mixture was purified by GPC (JAIGEL, CHCl
3
) to give a mixture of the trimer and a
) to give
1
pale yellow powder; mp 113–114 °C; H NMR (400 MHz, CDCl
3
)
3
1
d8.42 (s, 1H), 7.93 (dd, 1H, J = 8.8, 1.6 Hz), 7.71 (d, 1H, J = 8.8 Hz),
hexamer 6 as white solid (35 mg, 3ꢀ): mp >300 °C; H NMR
(400 MHz, CDCl ): d8.53 (s, 6 H), 8.22–7.25 (m, 24 H), 7.01 (s,
6 H), 5.83–5.71 (m, 6 H), 5.02–4.98 (m, 12 H), 4.33–4.28 (m, 6 H),
7
6
1
.59 (d, 1H, J = 8.4 Hz), 6.91 (dd, 1H, J = 8.8, 2.4 Hz), 6.79 (s, 1H),
3
.00 (m, 1H), 5.33 (dd, 1H, J = 15.6, 1.6 Hz), 5.22 (dd, 1H, J = 10.4,
1
3
13
.6 Hz), 4.20 (bs, 1H), 3.93 (s, 3H), 3.90 (d, 2H, J = 2.4 Hz);
) d167.7, 147.7, 137.8, 134.6, 131.0, 130.6,
26.2, 126.0, 125.8, 123.3, 118.4, 116.8, 104.1, 51.9, 46.2; IR (ATR
C
4.25–4.16 (m, 6 H); C NMR (400 MHz, CDCl
3
): d210.55, 198.23,
NMR (400 MHz, CDCl
1
system in CDCl
3
188.54, 170.21, 140.13, 130.20, 124.04, 127.36, 123.01, 117.76,
81.00, 64.55, 52.00, 30.06; IR (CDCl
3
): 3002, 2900, 1660,
À1
À1
3
) 3377, 2948, 1527, 1621, 1620, 1545 cm ; MS
1600 cm ; FAB-MS m/z 1254.50.
+
(
FAB) m/z 241 (M ); HRMS (FAB) m/z found 241.1120, Calcd. for
+
C
15
H16NO
2
(M ) m/z 241.1103; Anal. Calcd. for C15
2
H15NO : C,
2.6. 2,5,8-Tripropyl-2,5,8-triaza-1(2,6),4(2,6),7(2,6)-
7
4.67; H, 6.27; N, 5.81. Found: C, 74.48; H, 6.25; N, 5.98.
trisnaphthalenacyclononaphane-3,6,9-trione (7)
The Pd/C (34 mg) was added to a suspension of cyclic trimer 5
2
.3. 6-Allylamino-2-naphthoic acid (4)
(
342 mg, 0.3 mmol) in ethanol, and the mixture stirred for 10 h un-
der H atmosphere. The Pd/C was filtrated and the solvent was re-
moved under reduced pressure. The residue was purified by
recrystallization from CHCl to give 7 as white solid (131 mg,
0ꢀ): mp >300 °C; H NMR (400 MHz, CDCl ): d7.302 (s, 1H),
.288 (s, 1H), 7.230 (m, 4H), 7.198 (m, 4H), 7.121 (m, 6H), 6.997
2
To a solution of methyl 6-allylamino-2-naphthoate (1.51 g,
.27 mmol) in ethanol (47 mL) was added aqueous 4.0 M NaOH
6
3
(
15.7 mL) with stirring, and the reaction mixture was heated at
1
7
7
(
3
reflux for 1 h. The reaction mixture was cooled with ice-water
bath and was neutralized by aqueous 4.0 M HCl with cooling.
The precipitate collected by filtration, was 6-allylamino-2-naph-
thoic acid (4) (1.22 g, 86ꢀ): pale yellow powder; mp 189–
1
7
J = 8.8 Hz), 6.93 (dd, 1H, J = 8.8, 2.4 Hz), 6.81 (s, 1H), 6.00 (m,
1
3
s, 2H), 4.033 (m, 3H), 3.834 (m, 3H), 1.701 (br, 6H), 0.989 (t,
1
3
J = 7.2 Hz, 9H);
3
C NMR (400 MHz, CDCl ): d196.09, 179.73,
1
9
1
74.37, 160.09, 138.90, 137.18, 130.33, 127.95, 123.19, 106.83,
1
90 °C; H NMR (400 MHz, CDCl
3
(1ꢀ CD
3
OD)) d8.45 (s, 1H),
9.98, 48.80, 34.22, 24.10; IR (CDCl
602 cm ; FAB-MS m/z 633.30; ESI-HRMS m/z found 656.2878,
3
): 3058, 2919, 1645,
.94 (dd, 1H, J = 8.8, 2.0 Hz), 7.72 (d, 1H, J = 9.2 Hz), 7.60 (d, 1H,
À1
39 3 3
Calcd. for C42H N O Na m/z 656.2889.
H), 5.33 (dd, 1H, J = 1.6, 17.2 Hz), 5.22 (dd, 1H, J = 8.8, 1.6 Hz),
.91 (d, 1H, J = 8.8 Hz); 13C NMR (400 MHz, CDCl
(1ꢀ CD OD))
3
3
3
. Results and discussion
d169.7, 147.8, 144.9, 137.9, 134.6, 131.5, 130.6, 126.2, 125.8,
1
23.0, 118.4, 116.7, 104.0, 46.1; IR (ATR system in CDCl
3
) 3409,
3
.1. Synthesis of calix[3]amides 5 and 7
À1
+
1
675, 1618, 1496 cm ; MS (FAB) m/z 227 (M ); HRMS (FAB) m/
+
z found 227.1006, Calcd. for C14
Calcd. for C14 13NO : C, 73.99; H, 5.77; N, 6.16. Found: C, 73.77;
H, 5.65; N, 6.18.
2
H13NO (M ) m/z 227.0946; Anal.
The synthesis of the naphthalene ring-based cyclic trimer 5 is
H
2
shown in Scheme 1 [16–20]. After esterification of 6-amino-2-
naphthoic acid, the resulting methyl 6-amino-2-naphthoate was
N-allylated using 0.5 eq. of allyl bromide in HMPA at 80 °C for
2 h to give methyl 6-allylamino-2-naphthoate 3 in 61ꢀ yield
(based on allyl bromide). 6-Allylamino-2-naphthoic acid 4, which
was obtained by hydrolysis of 3, was successfully cyclized using
dichlorotriphenylphosphorane in 1,1,2,2-tetrachloroethane at
120 °C to give the cyclic trimer 5 as a major product (30ꢀ yield).
A cyclic hexamer (6) was also obtained as a by-product but was
not fully characterized. The corresponding N-propyl cyclic trimer
7 was synthesized by catalytic hydrogenation of 5 (Scheme 2) be-
cause sufficient refinement for the X-ray diffraction data of 5 could
not be obtained for crystals of 5 due to the disorder of the N-allyl
group.
2.4. 2,5,8-Triallyl-2,5,8-triaza-1(2,6),4(2,6),7(2,6)-
trisnaphthalenacyclononaphane-3,6,9-trione (5)
To a solution of 6-allylamino-2-natphthoic acid (4) (1.22 g,
.4 mmol) in 1,1,2,2,-tetrachloroethane (54 mL) under Ar was
5
added dichlorotriphenylphosphorane (4.32 g, 13.0 mmol) with
stirring for 6 h at 120 °C. The solvent was removed under reduced
pressure, and the residue was purified by column chromatography
on silica gel (eluent: CHCl
hexamer. The mixture was purified by GPC (JAIGEL, CHCl
3
) to give a mixture of the trimer and a
) to give
3
1
trimer 5 as white solid (342 mg, 30ꢀ): mp 263–264 °C; H NMR
400 MHz, CDCl ): d7.596 (s, 1 H), 7.538 (s, 1H), 7.336–7.408 (m,
H), 7.303 (s, 1H), 7.277 (d, J = 4 Hz, 1H), 7.233 (d, J = 4 Hz, 1H),
(
3
4
7
1
8
6
4
1
8
1
3.2. Crystal structure of 7
.188 (dd, J = 2.1, 8.6 Hz, 2H), 7.172 (s, 1H), 7.152 (t, J = 2.3 Hz,
H), 7.132 (d, J = 1.8 Hz, 1H), 7.100 (m, 1H), 7.068 (dd, J = 2.0,
.7 Hz, 1H), 6.998 (s, 1H), 6.998 (dd, J = 2.2, 8.7 Hz, 1H), 6.056–
.003 (m, 3H), 5.231–5.177 (m, 6H), 4.64–4.588 (m, 3H), 4.526–
X-ray single crystal analysis was carried out for crystals of 7
3
(Table 1), which were grown in CHCl solution. An ORTEP draw-
ing is shown in Fig. 1. The possible conformations of 7 are syn in
which three naphthalene rings are directed to the same sides
and anti in which one of the three naphthalene rings is directed
to the opposite side. Both conformations have molecular chirality
based on the directions of the amide bond and the naphthalene
ring (Fig. 2). The molecule in the crystal of 7 exists in the anti
conformation and as would be expected, has a larger cavity than
that of the corresponding benzene ring-containing calix[3]amide.
1
3
.475 (m, 3H);
3
C NMR (400 MHz, CDCl ): d213.65, 199.37,
88.65, 171.40, 140.75, 133.01, 129.14, 127.36, 123.19, 119.03,
3.80, 64.57, 52.37, 29.76; IR (CDCl
602 cm ; FAB-MS m/z 625.23; ESI-HRMS m/z found 648.2260,
3
): 3058, 2919, 1645,
À1
Calcd. for C42
C H N O
42 33 3 3
N, 6.63.
31 3 3
H N O Na m/z 648.2263. Elemental Anal. Calcd. for
: C, 80.36; H, 5.30; N, 6.69. Found: C, 80.14; H, 5.20;