¨
S¸.C¸ . Ozkan et al.
3
0
Anal. calcd for C64H82O8N2 (1007.34): C, 76.3; H, 8.2; N,
2.8. Found: C, 76.5; H, 8.1; N, 3.1.
127.5, 132.4, 134.0, 140.8, 141.5, 147.2, 149.5, 150.6,
152.0, 167.5 (CvO). FAB-MS m/z: 1106.27 (M þ Na)þ.
Anal. calcd for C70H86O8N2 (1083.44): C, 77.6; H, 8.0; N,
2.5. Found: C, 78.1; H, 7.8; N, 2.3.
4.2.4.2 Compound
o
6
C v
.
Y
i
e
1
l
d
6
5
%
.
M
p
l
:
1 0 0 –
1
0
2
C
.
I
R
:
1
6
5
0
c
m 21
(
O
).
H
N
M
R
(
C
D
C
)
: d ppm
3
0.93 (s, 18H, But), 1.29 (s, 18H, But), 1.73–2.14 (m, 16H,
OCH2CH2CH2 CH2CO, OCH2CH2CH2), 2.51 (t, 4H,
J ¼ 7.2 Hz, COCH2), 3.33 (d, 4H, J ¼ 13.1 Hz, ArCH2-
Ar), 3.39–3.52 (m, 4H, NHCH2), 3.66–3.76 (m, 4H,
OCH2), 3.88–4.06 (overlapped, 6H, OCH2, OCH), 4.25
(d, 4H, J ¼ 13.1 Hz, ArCH2Ar), 6.76 (s, 4H, ArH), 7.07–
7.11 (overlapped, 6H, ArH, OH), 7.37 (t, 2H, J ¼ 5.4 Hz,
NH). 13C NMR (CDCl3): d 23.8 (ArOCH2CH2CH2), 25.9
(CHCH2CH2), 29.0 (ArOCH2CH2), 31.2, 31.8, 31.9, 34.0,
34.3, 37.1 (NHCOCH2), 43.8 (NHCH2), 64.5 (CHOCH2),
66.8 (ArOCH2), 77.6 (NHCH2CH), 125.3, 125.7, 128.2,
132.6, 141.7, 146.5, 148.9, 150.2, 174.1 (CvO). FAB-MS
m/z: 1038.24 (M þ Na)þ. Anal. calcd for C64H90O8N2
(1015.41): C, 75.7; H, 8.9; N, 2.7%. Found: 75.5; H, 8.5;
N, 2.9%.
4.2.5 Synthesis of monoamide derivatives (7, 13)
A c i d c h l o r i d e c o m p o u n d o f c a l i x a r e n e ( 4 or 10) (3 mmol)
was dissolved in THF, 3-morpholinopropyl amine
(3 mmol) was added, the reaction mixture was stirred at
room temperature for 3 h. It was pured with same
procedure of 5, 6, 11 and 12.
o
4.2.5.1 Compound
0
7
.
Y
i
e
l
C v
d
7
5
%
.
M
p .
(
1
1
0
C
(
d
e
c
o
m
p
.
)
I
R
:
1
6
5
c
m 21
(
O
)
1
7
2
9
c
m 21
C
O
O
H
)
.
1
H
N
M
R
(
C
D
C
l
)
: d ppm 0.95 (s, 18H, But), 1.27 (s, 18H,
3
But), 1.93–2.12 (m, 10H, NHCH2CH2, COCH2CH2CH2),
2.40–2.60 (m, 4H, COCH2), 2.95–3.11 (m, 6H, N(CH2)3),
3.31 (d, 4H, J ¼ 13.1 Hz, ArCH2Ar), 3.41 (q, 2H,
J ¼ 6.6 Hz, NHCH2), 3.92–4.02 (m, 8H, ArOCH2,
CH2OCH2), 4.22 (d, 4H, J ¼ 13.1 Hz, ArCH2Ar), 6.72–
6.84 (m, 4H, ArH), 7.03–7.11 (m, 4H, ArH), 7.47 (s, 2H,
OH), 7.89 (t, 1H, J ¼ 5.4 Hz, NH). 13C NMR (CDCl3): d
22.8 (ArOCH2CH2CH2), 23.9 (ArOCH2CH2CH2), 29.3
(ArOCH2CH2), 29.5 (ArOCH2CH2), 30.3, 31.0, 31.5,
31.7, 33.8, 33.9, 34.0, 34.2, 36.0, 36.6, 52.1 (NHCH2),
55.4 (NCH2), 64.0 (CH2NCH2), 64.2 (CH2OCH2), 72.3
(ArOCH2), 125.5, 127.9, 128.2, 132.4, 133.4, 135.8, 142.1,
147.1, 149.7, 150.4, 150.8, 151.6, 174.5 (CvO), 177.1
(CvO). FAB-MS m/z: 998.17 (M þ Na)þ. Anal. calcd for
C61H86O8N2 (975.34): C, 75.1; H, 8.9; N, 2.9. Found: C,
75.7; H, 8.5; N, 2.6.
o
4.2.4.3 Compound 11
1
.
Y
i
e
l
d
6
3
%
.
M
p
:
2
2
6
–
2
2
9
C
.
I
R
:
1
6
3
9
c
m 21
(
C vO
)
.
H
N
M
R
(
C
D
C
l
)
: d ppm 0.92 (s,
3
18H, But), 1.30 (s, 18H, But), 3.34 (d, 4H, J ¼ 13.1 Hz,
ArCH2Ar), 4.28 (d, 4H, J ¼ 13.1 Hz, ArCH2Ar), 4.69 (d,
4H, J ¼ 11.5 Hz, NHCH2), 5.08 (s, 4H, OCH2), 6.25–6.34
(m, 4H, calix-ArH), 6.78 (s, 4H, calix-ArH), 7.07–7.09
(m, 6H, furfuryl-H), 7.34 (s, 2H, OH), 7.56 (t, 2H,
J ¼ 5.6 Hz, NH), 7.62 (d, 4H, J ¼ 8.4 Hz, ArH), 7.96 (d,
4H, J ¼ 8.4 Hz, ArH). 13C NMR (CDCl3): d 31.0 (CC H3),
31.5 (CC H3), 31.8 (ArCH2Ar), 33.9 (C(CH3)3), 34.1 (C
(CH3)3), 37.1 (NHCH2), 63.5 (OCH2), 107.4 (furfuryl
vCH), 110.6 (furfuryl vCH), 125.2, 125.7, 126.8, 127.6,
127.8, 132.3, 133.6, 140.9, 141.6, 142.0, 147.4, 149.6,
150.7, 152.0, 167.5 (CvO). FAB-MS m/z: 1098.21
(M þ Na)þ. Anal. calcd for C70H78O8N2 (1075.38): C,
78.1; H, 7.3, N, 2.6. Found: C, 77.6; H, 7.5, N, 2.2.
o
4.2.5.2 Compound 13
c
.
Y
i
e
C v
l
d
7
1
0
%
.
M
p .
(
1
5
5
C
(
d
e
c
o
m
p
.
)
.
I
R
:
1
6
4
0
m 21
(
O
)
7
1
3
c
m 21
C
O
O
H
)
.
1
t
H
N
M
R
(
C
D
C
l
)
:
d
p
p
m
0
.
9
1
(
s
,
1
8
H
,
B
u
)
,
1
.
2
9
(
s
,
1
8
H
,
3
But), 2.26–2.28 (m, 2H, CH2CH2CH2), 2.32 (t, 2H,
J ¼ 5.4 Hz, NCH2) 2.94–3.47 (overlapped, 10H, NHCH2,
CH2NCH2O, ArCH2Ar), 4.05 (bs, 4H, CH2OCH2), 4.27
(d, 4H, J ¼ 13.3 Hz, ArCH2Ar), 5.08 (s, 4H, OCH2),
6.75–6.81 (m, 4H, ArH), 7.02–7.14 (overlapped, 6H,
ArH, OH), 7.81 (d, 4H, J ¼ 8.0 Hz, ArH), 8.09 (d, 4H,
J ¼ 8.0 Hz, ArH), 8.67 (t, 1H, J ¼ 5.2 Hz, NH) 13C NMR
(CDCl3): d 23.8 (NHCH2CH2), 29.5, 30.3, 30.9, 31.7,
33.8, 33.9, 34.2, 37.2 (NHCH2), 52.1, 55.5 (NCH2), 60.1
(CH2NCH2), 60.9 (CH2OCH2), 63.7 (OCH2), 125.0,
125.5, 125.6, 126.6, 127.0, 127.6, 127.9, 128.2, 129.9,
132.3, 132.5, 133.0, 135.8, 141.3, 141.6, 142.1, 147.3,
149.5, 150.5, 151.4, 166.4 (CvO), 167.9 (CvO). FAB-
MS m/z: 1066.21 (M þ Na)þ. Anal. calcd for C67H82O8N2
(1043.38): C, 77.1; H, 7.9; N, 2.7. Found: C, 76.7; H, 8.1;
N, 2.5.
o
4.2.4.4 Compound 12
1
.
Y
i
e
l
d
6
0
%
.
M
p
:
1
5
0
–
1
5
3
C
.
I
R
:
1
6
5
7
c
m 21
(
C
v
O
)
.
H
N
M
R
(
C
D
C
l
)
: d ppm 0.93 (s,
3
18H, But), 1.29 (s, 18H, But), 1.59–1.77 (m, 4H
OCH2CH2), 1.86–1.98 (m, 4H, OCHCH2), 3.31 (d, 4H,
J ¼ 13.0 Hz, ArCH2Ar), 3.44–3.54 (m, 2H, NHCH2),
3.73–3.84 (m, 4H, OCH2), 3.86–3.95 (m, 2H, NHCH2),
4.14 (p, 2H, J ¼ 5.4 Hz, OCH), 4.27 (d, 4H, J ¼ 13.0 Hz,
ArCH2Ar), 5.09 (s, 4H, OCH2Ar), 6.78 (s, 4H, calix-ArH),
7.05 (s, 4H, calix-ArH), 7.13 (s, 2H, OH), 7.28 (t, 2H,
J ¼ 5.4 Hz, NH), 7.75 (d, 4H, J ¼ 8.3 Hz, ArH), 7.91 (d,
4H, J ¼ 8.4 Hz, ArH). 13C NMR (CDCl3): d 25.9
(OCH2CH2), 28.9, 30.9, 31.6, 31.7, 33.8, 33.9, 43.8
(NHCH2), 68.2, 68.4, 77.9 (OCH), 125.0, 125.6, 126.8,