870
E. Tiftikçi and Ç. Erk
Vol. 41
5.0 mmol) [18], K CO (1.38 g, 10.0 mmol) and DMF (25 mL)
reacted at 70-80 C for 70-80 h while stirring. The crude product,
190, 73; for C
422,1949.
H
O HRMAS Calcd, 422,1941; found
8
2
3
22 30
o
treated as described above, was purified by column chromatogra-
14-Ethyl-15-methyl-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]tetra-
oxacyclododecino[2,3-h]chromen-13-one (6a).
o
phy (Al O /CH Cl ) to afford 5c, 0.20 g (10 %), mp 90 C; IR
2
3
2
2
-1
1
(KBr) 2937, 1705, 1110, 762 cm ; H NMR (CDCl 400 MHz):
3
Compound 3d (1.10 g, 5.0 mmol), 4a (0.94 g, 5.0 mmol) and
δ 1.10 (3H, t, CH ), 2.34 (3H, s, CH ), 2.64 (2H, q, CH ), 3.65
3
3
2
Na CO (1.06 g, 10.0 mmol) and DMF (25 mL) treated as
(4H, m, C H O), 3.69 (4H, m, 2CH ), 3.74 (4H, m, 2CH ), 3.92
2
3
2
4
2
2
o
described above to afford 6a, 0.36 g (18 %), mp 120 C; IR (KBr)
(4H, t, 2CH ), 4.17 (4H, t, 2CH ), 6.75 (1H, s, Ar), 6.97 (1H, s,
2
2
-1
1
13
2990, 1710, 1450, 1150, 750 cm ; H NMR (CDCl 400 MHz):
Ar); C NMR (CDCl 100 MHz): δ 13.0, 14.6, 20.8, 69.1, 69.3,
3
3
69.7, 69.8, 70.6, 70.7, 70.8, 70.8, 70.9, 71.0, 101.5, 110.0, 113.7,
δ 1.11 (3H, t, CH ), 2.35 (3H, s, CH ), 2.63 (2H, q, CH ), 3.83
3 3 2
+
+
125.5, 145.3, 148.2, 152.0, 161.9: ms; m/z 422(M ), 246(M -
C H O , 233, 203, 190; for C O HRMAS Calcd, 422.1941;
(6H, m, 3CH ), 3.96 (2H, t, CH ), 4.20 (2H, t, CH ), 4.35 (2H, t,
2 2 2
13
H
CH ), 6.82 (1H, d, Ar), 7.23 (1H, d, Ar): C NMR (CDCl 100
4
8
2
22 30
8
2
3
found 422.1941.
MHz): δ 13.1, 14.6, 20.8, 69.4, 69.7, 69.9, 70.3, 70.6, 74.9, 109.9,
115,6, 119.0, 125.2, 136.0, 145.4, 146.3, 153.6, 160.2: ms; m/z
15-Propyl-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]tetraoxacy-
clododecino[2,3-g]chromen-13-one (5d).
+
+
334 (M ), 246 (M -2x44), 236, 203; for C
Calcd, 334.1416; found, 334.1413.
H O HRMAS
18 22 6
Compound 3a (1.10 g, 5.0 mmol), 4a (0.94 g, 5.0 mmol) and
17-Ethyl-18-methyl-2,3,5,6,8,9,11,12-octahydro-15H-
[1,4,7,10,13]pentaoxacyclopentadecino[2,3-h]-chromen-15-one
(6b).
Na CO (1.06 g, 10.0 mmol) reacted in DMF (25 mL) at 70-80
2
3
o
C for 70-80 h while stirring. The crude product, treated as
described above, was purified by column chromatography
o
(Al O /CH Cl ) to afford 5d, 0.10 g (7 %), mp 115 C; IR (KBr)
Compound 3d (1.10 g, 5.0 mmol), 4b (1.15 g, 5.0 mmol) and
2
3
2
2
-1
1
2940, 1725, 1103, 760 cm ; H NMR (CDCl 400 MHz): δ 1.00
Na CO (1.06 g, 10.0 mmol) and DMF (25 mL) treated as
3
2
3
o
(3H, t, CH ), 1.64 (2H, m, CH ), 2.63 (2H, t, CH ), 3.66 (4H, m,
described above to afford 6b, 0.08 g (4 %), mp 105 C; IR (KBr)
2985, 1725, 1107, 770 cm ; H NMR (CDCl 400 MHz): δ 1.11
3
2
2
-1
1
2CH ), 3.82 (4H, t, 2CH ), 4.08 (4H, s, 2CH ), 5.97 (1H, s,
2
2
2
3
13
cumH), 6.65 (1H, s, ArH), 6.88 (1H, s, ArH): C NMR (CDCl
(3H, t, CH ), 2.35 (3H, s, CH ), 2.63 (2H, q, CH ), 3.91 (8H, m,
3
3
3
2
100 MHz): δ 13.9, 21.3, 33.8, 69.1, 69.3, 69.8, 70.7, 70.9, 71.5,
2CH ), 4.01 (4H, m, 2CH ), 4.27 (2H, tCH ), 4.37 (2H, t, CH ),
2
2
2
2
13
102.5, 108.7, 110.0, 119.9, 154.2, 150.5, 153.6, 155.5, 161.0: ms;
7.06 (1H, d, ArH), 7.20 (1H, d, ArH): C NMR (CDCl 100
3
+
+
m/z 334 (M ), 246 (M -2x44), 231, 218, 203, 188, 73; for
O HRMAS Calcd, 334,1416: found 334.1411.
MHz): δ 13.1, 14.5, 20.7, 69.3, 69.7, 69.9, 70.2, 70.6, 71.4, 72.0,
C
H
74.8, 109.9, 115.6, 119.0, 125.2, 136.0, 145.4, 146.4, 153.6,
18 22
6
+
+
160.2 ms; m/z 378 (M ), 246 (M -C H O ), 218, 196, 73; for
4
8 2
18-Propyl-2,3,5,6,8,9,11,12-octahydro-15H-[1,4,7,10,13]pen-
taoxacyclopentadecino[2,3-g]chromen-15-one (5e).
C
H O HRMAS Calcd, 378.1679: found 378.1672.
20 26 7
20-Ethyl-21-methyl-2,3,5,6,8,9,11,12,14,15-nonahydro-18H-
[1,4,7,10,13,16]hexaoxacyclooctadecino[2,3-h]-chromen-18-one
(6c).
Compound 3a (1.10 g, 5.0 mmol), 4b (1.15 g, 5.0 mmol) and
Na CO (1.06 g, 10.0 mmol) reacted in DMF (25 mL) at 70-80
2
3
o
C for 70-80 h while stirring. The crude product, treated as
described above, was purified by column chromatography to
Compound 3d (1.10 g, 5.0 mmol), 4c (2.51 g, 5.0 mmol) [18]
o
afford 5e, 0.1 g (5 %), mp 100 C; IR (KBr) 2935, 1720, 1136,
and K CO (1.38 g, 10.0 mmol) and DMF (25 mL) treated as
2
3
-1
1
o
765 cm ; H NMR (CDCl 400 MHz): δ 1.13 (3H, t, CH ), 1.69
described above to afford 6c, 0.48 g (23 %), mp 78 C; IR (KBr)
2945, 1700, 1105, 760 cm ; H NMR (CDCl 400 MHz): δ 1.11
3
3
-1
1
(2H, m, CH ), 2.66 (2H, t, CH ), 3.56 (8H, m, 4CH ), 3.82 (4H,
2
2
2
3
m, 2CH ), 4.06 (4H, m, 2CH ), 6.08 (1H, s, cumH), 6.65 (1H, s,
(3H, t, CH ), 2.37 (3H, s, CH ), 2.60 (2H, q, CH ), 3.69 (8H, m,
2
2
3
3
2
13
ArH), 6.88 (1H, s, ArH): C NMR (CDCl 100 MHz): δ 14.0,
4CH ), 3.75 (4H, m, 2CH ), 3.90 (2H, t, CH ) 3.97 (2H, t, CH ),
3
2
2
2
2
21.3, 33.8, 69.4, 69.8, 70.4, 71.0, 71.2, 71.4, 71.8, 71.9, 102.3,
108.7, 110.0, 112.2, 146.1, 150.4, 153.5, 155.4, 161.7: ms; m/z
4.19 (2H, t, CH ), 4.28 (2H, t, CH ), 6.83 (1H, d, ArH), 7.26 (1H,
2
2
13
d, ArH): C NMR (CDCl 100 MHz): δ 13.1, 14.5, 20.8, 68.6,
3
+
+
378 (M ), 334, 246 (M -C H O ), 218, 141, 71. for C
H O
69.1, 69.9, 70.0, 70.1, 70.2, 70.5, 70.7, 70.8, 73.4, 108.7, 115,6,
118.9, 125.2, 135.3, 145.4, 146.3, 153.5, 160.2: ms; m/z 422
4
8
2
20 26 7
HRMAS Calcd, 378.1679; found, 378.1681.
+
+
(M ), 334, 246 (M -C H O ), 231, 218, 190, 73; for C
H O
4
8
2
22 30 8
2 1 - P r o p y l - 2 , 3 , 5 , 6 , 8 , 9 , 11 , 1 2 , 1 4 , 1 5 - n o n a h y d r o -
18H[1,4,7,10,13,16]hexaoxacyclooctadecino[2,3-g]chromen-
18-one (5f).
HRMAS Calcd, 422.1941; found 422.1951.
15-Propyl-2,3,5,6,8,9-hexahydro-13H-[1,4,7,10]tetraoxacyclo-
dodecino[2,3-h]chromen-13-one (6d).
Compound 3a (1.10 g, 5.0 mmol), 4c (2.51 g, 5.0 mmol) [18]
and K CO (1.38 g, 10.0 mmol) reacted in DMF (25 mL) at 70-
Compound 3c (1.10 g, 5.0 mmol), 4a (0.94 g, 5.0 mmol) and
2
3
o
80 C for 60-70 h while stirring. The crude product, treated as
described above, was purified by column chromatography to
Na CO (1.06 g, 10.0 mmol) and DMF (25 mL) treated as
2
3
o
described above to afford 6d, 0.39 g (23 %), mp 72 C; IR (KBr)
2935, 1725, 1107, 770 cm ; H NMR (CDCl 400 MHz): δ 1.02
o
-1
1
afford 5f 0.12g (7 %), mp 85 C, IR (KBr) 2935, 1720,1130, 850
3
-1 1
cm ; H NMR (CDCl 400 MHz): δ 1.05 (3H, t, CH ), 1.70 (2H,
(3H, t, CH ), 1.71 (2H, m, CH ), 2.67 (2H, t, CH ), 3.80 (4H, s,
3
3
3 2 2
m, CH ), 2.65 (2H, t, CH ), 3.70 (4H, m, 2CH ), 3.76 (8H, m,
2CH ), 3.95 (4H, m, 2CH ), 4.19 (2H, t, CH ), 4.28 (2H, t, CH ),
2 2 2 2
2
2
2
13
2CH ), 3.94 (4H, t, CH ), 4.19 (4H, t, CH ), 6.12 (1H, s, cumH),
6.12 (1H, s, cumH), 6.80 (1H, d, ArH), 7.10 (1H, d, ArH)):
C
2
2
2
13
6.80 (1H, s, ArH), 7.01 (1H, s, ArH): C NMR (CDCl 100
NMR (CDCl 100 MHz): δ 13.9, 21.5, 33.8, 69.4, 69.6, 70.2, 70.5,
3
3
MHz): δ 13.9, 21.3, 33.8, 68.8, 69.0, 69.5, 70.1, 70.5, 70.6, 70.6,
70.6, 71.9, 109.9, 110.6, 114.2, 119.0, 136.4, 147.9, 154.7, 156.1,
+
+
70.7, 70.7, 70.8, 101.4, 108.9, 110.9, 111.9, 145.3, 149.7, 152.5,
160.4: ms; m/z 334(M ), 306, 246 (M -C H O ), 231, 218, 203;
4 8 2
+
+
155.6, 161.3: ms; m/z 422 (M ), 334, 246 (M -C H O , 218,
for C H O HRMAS Calcd, 334.1416; found 334.1418.
18 22 6
4
8
2