6892 J . Org. Chem., Vol. 61, No. 20, 1996
Pastushok et al.
469 [M + 1]+. Anal. Calcd for C24H35Cl2N3O2: C, 61.53; H,
7.53. Found: C, 61.63; H, 7.46.
was isolated as an oil after column chromatography on Al2O3
using 3/1 CHCl3/THF as eluant: 1H NMR δ 0.99 (t, J ) 7.3
Hz, 6 H), 1.02 (t, J ) 7.4 Hz, 6 H), 2.52 (m, 20 H), 3.54 (s, 4
H), 3.78 (s, 4 H), 3.88 (t, J ) 5.5 Hz, 4 H), 4.10 (t, J ) 5.5 Hz,
4 H), 7.08 (m, 6 H); MS, m/z 653 (M+). Anal. Calcd for
C34H54Cl2N4O4: C, 62.47; H, 8.33. Found: C, 62.57; H, 8.12.
16,33-Dich lor o-35,36-d ih yd r oxy-3,6,9,12,20,23,26,29-oc-
ta eth yl-3,6,9,12,20,23,26,29-octa a za tr icyclo[29.3.1.114,18]-
h exa t r ia con t a -1(35),14,16,18(36),31,33-h exa en e
(10)
(Sch em e 3). Compound 10 was synthesized as above for 7
from 0.24 g (8 mmol) of paraformaldehyde, 1.0 g (4 mmol) of
1,4,7,10-tetraethyl-1,4,7,10-tetraazadecane, and 2.1 g (4 mmol)
of bisphenol 13. Crude 10 was purified on silica gel with 15/1
and 4/1 CH3OH/NH4OH as eluants. The solvents were evapo-
rated under reduced pressure. The residue was dissoved in
100 mL of benzene, and the solution was dried (Na2SO4) and
evaporated to give 1.26 g (40%) of 10 as an oil: 1H NMR δ
1.00 (t, J ) 7.5 Hz, 12 H), 1.18 (t, J ) 7.5 Hz, 12 H), 2.56 (m,
40 H), 3.62 (s, 8 H), 7.03 (s, 4 H); MS, m/z 412 [M/2 + 1]+. Anal.
Calcd for C44H78Cl2N8O2: C, 64.29; H, 9.56. Found: C, 63.98;
H, 9.36.
13,27-Dich lor o-29,30-d ih yd r oxy-3,9,17,23-tetr a m eth yl-
6,20-dioxa-3,9,17,23-tetr aazatr icyclo[23.3.1.111,15]tr iacon ta-
1(29),11,13,15(30),25,27-h exa en e (11) (Sch em e 3). Com-
pound 11 was synthesized as above for 7 from 1.14 g (0.038
mol) of paraformaldehyde, 2.5 g (0.019 mol) of 1,7-dimethyl-
4-oxa-1,7-diazaheptane, and 7.84 g (0.019 mol) of bisphenol
14. After column chromatography on silica gel using 40/1
MeOH/NH4OH as eluant, the solvents were evaporated and
the residue was dissolved in 150 mL of benzene. The solution
was dried (Na2SO4), filtered, and evaporated under reduced
pressure. To the residue was added 70 mL of EtOEt. The
pure product was precipitated, filtered, and washed with
EtOEt to give 1.1 g (10%) of 11 as a solid: mp 150-152 °C;
1H NMR δ 2.3 (s, 12 H), 2.68 (t, J ) 5.6 Hz, 8 H), 3.55 (t, J )
5.6 Hz, 8 H), 3.60 (s, 8 H), 6.99 (s, 4 H); MS, m/z 570 [M + 1]+.
Anal. Calcd for C28H42Cl2N4O4: C, 59.04; H, 7.33. Found: C,
59.05; H, 7.32.
18,35-Dich lor o-22,25,28,31-t et r a et h yl-2,5,8,11,14-p en -
t a o x a -2 2 ,2 5 ,2 8 ,3 1 -t e t r a a z a t r i c y c l o [3 1 .4 .0 .0 1 5 , 2 0 ]-
h eptatr iacon ta-1(33),15,17,19,34,36-h exaen e (28) (Sch em e
5). Compound 28 was obtained in the same manner as above
for 25 from 1.95 g (3.6 mmol) of 13, 1.82 g (3.6 mmol) of
tetraethyelene glycol ditosylate, and 10 g (0.072 mol) of K2-
CO3. 28 (0.18 g, 7%) was isolated as an oil after column
chromatography on Al2O3 using THF as eluant: 1H NMR δ
1.00 (t, J ) 7.5 Hz, 6 H), 1.03 (t, J ) 7.4 Hz, 6 H), 2.50 (m, 20
H), 3.55 (s, 4 H), 3.69 (s, 8 H), 3.82 (t, J ) 5.2 Hz, 4 H), 4.06
(t, J ) 5.2 Hz, 4 H), 7.06 (m, 6 H); MS, m/z 698 [M + 1]+.
Anal. Calcd for C36H58Cl2N4O5: C, 61.97; H, 8.38. Found: C,
61.81; H, 8.22.
12,26-Dich lor o-16,22-d im eth yl-2,5,8,19-tetr a oxa -16,22-
d ia za t r icyclo[22.4.0.09,14]oct a cosa -1(24),9,11,13,25,27-
h exa en e (29) (Sch em e 5). Compound 29 was synthesized
as above for 25 from 2.1 g (5 mmol) of 14, 2.11 g (5 mmol) of
diethylene glycol ditosylate, and 13.8 g (0.1 mol) of K2CO3. 29
(1.06 g, 43%) was isolated as an oil after column chromatog-
raphy on Al2O3 using 5/1 CHCl3/THF as eluant: 1H NMR δ
2.25 (s, 6 H), 2.75 (t, J ) 5.8 Hz, 4 H), 3.61 (s, 4 H), 3.69 (t, J
) 5.8 Hz, 4 H), 3.98 (t, J ) 5.5 Hz, 4 H), 4.14 (t, J ) 5.5 Hz,
4 H), 6.98 (m, 6 H); MS, m/z, 484 [M + 1]+. Anal. Calcd for
C
24H32Cl2N2O4: C, 59.63; H, 6.67. Found: C, 59.50; H, 6.53.
15,32-Dich lor o-19,28-d im eth yl-2,5,8,11,22,25-h exa oxa -
19,28-d ia za t r icyclo[28.4.0.012,17]t et r a t r ia con t a -1(30),12,-
14,16,31,33-h exa en e (30) (Sch em e 5). Compound 30 was
obtained in the same manner as above for 25 from 2.27 g (5
mmol) of 15, 2.28 g (5 mmol) of triethylene glycol ditosylate,
and 13.8 g (0.1 mol) of K2CO3. 30 (1.78 g, 62%) was isolated
after column chromatography on Al2O3 using 1/1 CHCl3/THF
as eluant: mp 75-78 °C; 1H NMR δ 2.23 (s, 6 H), 2.75 (t, J )
5.7 Hz, 4 H), 3.69 (m, 16 H), 3.85 (t, J ) 5.6 Hz, 4 H), 4.08 (t,
J ) 5.6 Hz, 4 H), 6.95 (m, 6 H); MS, m/z 572 [M +1]+. Anal.
Calcd for C28H40Cl2N2O6: C, 58.84; H, 7.05. Found: C, 59.00;
H, 7.22.
16,33-Dich lor o-35,36-d ih ydr oxy-3,12,20,29-tetr a m eth yl-
6,9,23,26-tetr a oxa -3,12,20,29-tetr a a za tr icyclo[29.3.1.114,18]-
h exa t r ia con t a -1(35),14,16,18(36),31,33-h exa en e
(12)
(Sch em e 3). Compound 12 was prepared as above for 7 from
0.85 g (0.028 mol) of paraformaldehyde, 2.5 g (0.014 mol) of
1,10-dimethyl-4,7-dioxa-1,10-diazadecane, and 6.49 g (0.014
1
mol) of bisphenol 15 to give 1.8 g (20%): mp 108-110 °C; H
NMR δ 2.25 (s, 12 H), 2.67 (t, J ) 5.7 Hz, 8 H), 3.64 (m, 24 H),
7.02 (s, 4 H); MS, m/z 658 [M + 1]+. Anal. Calcd for C32H50
Cl2N4O6: C, 58.44; H, 7.66. Found: C, 58.52; H, 7.67.
-
12,26-Dich lor o-16,19,22-t r iet h yl-2,5,8-t r ioxa -16,19,22-
t r ia za t r icyclo[22.4.0.09,14]oct a cosa -1(24),9,11,13,25,27-
h exa en e (25) (Sch em e 5). A mixture of 1.45 g (3 mmol) of
16, 1.28 g (3 mmol) of diethylene glycol ditosylate, 8.5 g (0.06
mol) of K2CO3, and 50 mL of CH3CN was stirred under reflux
for 72 h. The solvent was evaporated under reduced pressure,
and 100 mL of hot H2O was added to the residue. After being
cooled to rt, the mixture was extracted three times with 50-
mL portions of CHCl3, and the organic phase was separated,
dried (Na2SO4), and evaporated. The crude product was
purified on neutral Al2O3 using 20/1 CHCl3/THF as eluant to
give 0.6 g (36%) of 25 as an oil: 1H NMR δ 1.02 (t, J ) 7.5 Hz,
3 H), 1.08 (t, J ) 7.6 Hz, 6 H), 2.51, (m, 14 H), 3.6 (s, 4 H),
3.57 (t, J ) 5.0 Hz, 4 H), 4.14 (t, J ) 5.0 Hz, 4 H), 7.07 (m, 6
H); MS, m/z 539 [M + 1]+. Anal. Calcd for C28H41Cl2N3O3:
C, 62.45; H, 7.67. Found: C, 62.28; H, 7.59.
12,29-Dich lor o-16,19,22,25-t et r a et h yl-2,5,8-t r ioxa -16,-
19,22,25-tetr a a za tr icyclo[25.4.0.09,14]u n tr ia con ta -1(27),9,-
11,13,28,30-h exa en e (26) (Sch em e 5). Compound 26 was
synthesized in the same manner as above for 25 from 1.58 g
(3 mmol) of 13, 1.21 g (3 mmol) of diethylene glycol ditosylate,
and 8.3 g (0.06 mol) of K2CO3. 26 (0.6 g, 33%) was isolated as
an oil after column chromatography on Al2O3 using 10/1 CHCl3/
THF as eluant: 1H NMR δ 1.04 (m, 12 H), 2.53 (m, 20 H),
3.59 (s, 4 H), 3.97 (t, J ) 5.1 Hz, 4 H), 4.12 (t, J ) 5.1 Hz, 4
H), 7.10 (m, 6 H); MS, m/z 610 [M + 1]+. Anal. Calcd for
C32H50Cl2N4O3: C, 63.04; H, 8.27. Found: C, 62.98; H, 8.16.
15,32-Dich lor o-19,22,25,28-tetr a eth yl-2,5,8,11-tetr a oxa -
19,22,25,28-t et r a a za t r icyclo[28.4.0.012,17]t et r a t r ia con t a -
1(30),12,14,16,31,33-h exa en e (27) (Sch em e 5). Compound
27 was obtained in the same manner as above for 25 from 1.78
g (3.3 mmol) of 13, 1.51 g (3.3 mmol) of triethylene glycol
ditosylate, and 9.1 g (0.066 mol) of K2CO3. 27 (0.22 g, 10%)
13,27-Dich lor o-3,9,17,23-tetr a m eth yl-6,20,30,33,36-p en -
t a oxa -3,9,17,23-t e t r a a za t e t r a cyclo[23.3.1.729,37.111,15]-
h ep t a t r ia con t a -1(28),11,13,15(37),25,27-h exa en e (32)
(Sch em e 7). Compound 32 was obtained as described above
for 25 from 1.07 g (2 mmol) of crown compound 11, 0.78 g (2
mmol) of diethylene glycol ditosylate, and 5.5 g (40 mmol) of
K2CO3. Cryptand 32 (0.85 g, 71%) was isolated as an oil after
column chromatography on silica gel using 40/1 and 20/1
MeOH/NH4OH as eluants: 1H NMR δ 2.24 (s, 12 H), 2.70 (t,
J ) 5.7 Hz, 8 H), 3.55 (m, 16 H), 3.87 (t, J ) 5.1 Hz, 4 H), 4.20
(t, J ) 5.1 Hz, 4 H), 7.20 (s, 4 H); MS, m/z 640 [M + 1]+. Anal.
Calcd for C32H48Cl2N4O5: C, 60.09; H, 7.56. Found: C, 60.12;
H, 7.66.
9 , 1 2 , 1 5 , 2 6 , 2 9 , 3 4 , 3 7 , 4 0 , 4 3 , 4 6 - D e c a o x a - 1 , 2 3 -
diazapen tacyclo[21.8.8.77,17.016,21.03,8]h exatetr acon ta-3,5,7,-
16,18,20-h exa en e (33) (Sch em e 7). Compound 33 was
obtained as described above for 25 from 1 g (1.7 mmol) of
cryptand 3 (n ) 1), 0.72 g (1.7 mmol) of diethylene glycol
ditosylate, and 5 g (0.035 mol) of K2CO3. Cryptand 33 (0.24
g, 21%) was isolated as a solid (mp 147-150 °C) after column
chromatography on neutral Al2O3 using 40/1 MePh/MeOH as
eluant: 1H NMR δ 2.70 (m, 8 H), 3.53 (m, 20 H), 4.14 (m, 16
H), 6.83 (m, 6 H); MS, m/z 647 [M + 1]+. Anal. Calcd for
C
34H50N2O10: C, 63.14; H, 7.79. Found: C, 63.27; H, 7.68.
Ack n ow led gm en t. This work was supported by the
Department of Energy, Office of Basic Energy Sciences,
Contract DE-FG02-86ER 13463.
J O9607931