3524 J . Org. Chem., Vol. 65, No. 11, 2000
Park and Kurth
Eth yl cis-6-Aza -5-oxa -7-p h en yl-2-{[ben zyla m in o]-ca r -
bon yla m in o}sp ir o[3.4]oct-6-en -2-ca r boxyla te (17c) fr om
16c. As with 16a f 17a , compound 16c (71 mg, 0.26 mmol)
and benzyl isocyanate (35 mg, 0.26 mmol) gave compound 17c
(100 mg, 0.25 mmol, 96%) as a solid: Mp 185 °C; FTIR (KBr)
1727, 1625 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.56-7.54 (m,
2H), 7.42-7.24 (m, 3H), 7.17-7.12 (m, 5H), 6.16 (s, 1H), 5.86
(t, 1H, J ) 5.3 Hz), 4.23 (d, 2H, J ) 5.3 Hz), 4.16 (q, 2H, J )
7.0 Hz), 3.47 (s, 2H), 2.95 (d, 2H, J ) 13.4 Hz), 2.74 (d, 2H,
J ) 13.4 Hz), 1.22 (t, 3H, J ) 7.0 Hz); 13C NMR (75 MHz,
CDCl3) δ 174.2, 157.6, 157.4, 139.5, 130.1, 129.2, 128.6, 128.3,
127.1, 126.9, 126.5, 81.2, 61.5, 50.6, 47.1, 46.5, 43.8, 14.1.
Eth yl cis-6-Aza-7-(4-br om oph en yl)-2-{[(4-ch lor oph en yl)-
a m in o]ca r bon yla m in o}-5-oxa sp ir o[3.4]oct-6-en -2-ca r box-
yla te (17d ) fr om 16a . As with 16a f 17a , compound 16a
(92 mg, 0.26 mmol) and p-chlorophenyl isocyanate (80 mg, 0.26
mmol) gave compound 17d (127 mg, 0.25 mmol, 97%) as a
solid: Mp 243-244 °C; FTIR (KBr) 1729, 1641 cm-1; 1H NMR
(300 MHz, acetone-d6) δ 8.55 (s, 1H), 7.62 (s, 4H), 7.48 (d, 2H,
J ) 7.2 Hz), 7.21 (d, 2H, J ) 7.2 Hz), 6.94 (s, 1H), 4.19 (q, 2H,
J ) 7.1 Hz), 3.64 (s, 2H), 3.07 (d, 2H, J ) 13.2 Hz), 2.72 (d,
2H, J ) 13.2 Hz), 1.26 (t, 3H, J ) 7.1 Hz); 13C NMR (75 MHz,
acetone-d6, DMSO-d6) δ 174.8, 157.5, 155.8, 140.8, 133.1, 130.7,
130.4, 129.7, 126.8, 124.7, 120.6, 83.1, 62.2, 51.8, 48.0, 47.1,
15.0.
gave compound 18b (80 mg, 0.24 mmol, 92%) as a solid: Mp
162 °C; FTIR (KBr) 1804, 1720 cm-1 1H NMR (300 MHz,
;
CDCl3) δ 7.48-7.35 (m, 5H), 7.30 (s, 1H), 3.34 (s, 2H), 3.05 (d,
2H, J ) 12.2 Hz), 2.90 (d, 2H, J ) 12.2 Hz), 2.35 (t, 2H, J )
7.4 Hz), 1.55 (m, 2H), 1.35 (m, 2H), 0.92 (t, 3H, J ) 7.2 Hz);
13C NMR (75 MHz, CDCl3) δ 176.0, 160.6, 154.8, 131.5, 129.0,
128.0, 125.9, 77.7, 53.4, 48.1, 46.9, 28.2, 27.4, 22.2, 13.6. Anal.
Calcd for C18H21N3O3: C, 66.03; H, 6.46; N, 12.83. Found: C,
66.24; H, 6.46; N, 12.61.
cis-2,4,9-Tr iaza-8-oxa-10-ph en yl-2-ben zyldispir o-[4.1.4.1]-
d od ec-9-en -1,3-d ion e (18c) fr om 17c. As with 17a f 18a ,
compound 17c (100 mg, 0.24 mmol) and Na (6.7 mg, 0.29
mmol) gave compound 18c (84 mg, 0.23 mmol, 95%) as a
solid: Mp 203-204 °C; FTIR (KBr) 1794, 1712 cm-1; 1H NMR
(300 MHz, CDCl3) δ 7.70-7.67 (m, 2H), 7.41-7.39 (m, 5H),
7.35-7.25 (m, 4H), 4.67 (s, 2H), 3.76 (s, 2H), 3.09 (d, 2H, J )
14.0 Hz), 2.92 (d, 2H, J ) 14.0 Hz); 13C NMR (75 MHz, CDCl3)
δ 176.7, 157.7, 155.8, 135.9, 130.4, 129.0, 128.8, 128.7, 128.4,
127.9, 126.7, 79.1, 53.6, 46.8, 45.8, 42.2. Anal. Calcd for
C
21H19N3O3: C, 69.79; H, 5.29; N, 11.62. Found: C, 70.16; H,
5.46; N, 11.37.
cis-2,4,9-Tr iaza-10-(4-br om oph en yl)-2-(4-ch lor oph en yl)-
8-oxa d isp ir o[4.1.4.1]d od ec-9-en -1,3-d ion e (18d ) fr om 17d .
As with 17a f 18a , compound 17d (100 mg, 0.19 mmol) and
sodium (6 mg, 0.23 mmol) gave compound 18d (82 mg, 0.18
mmol, 93%) as a solid: Mp 257-258 °C; FTIR (KBr) 1774, 1719
cm-1; 1H NMR (300 MHz, DMSO-d6) δ 7.66-7.41 (m, 9H), 3.73
(s, 2H), 3.01 (d, 2H, J ) 13.8 Hz), 2.84 (d, 2H, J ) 13.8 Hz);
13C NMR (75 MHz, DMSO-d6) δ 175.7, 157.0, 154.3, 132.3,
132.1, 131.2, 128.9, 128.7, 128.5, 123.7, 79.3, 53.0, 46.8, 45.1.
Anal. Calcd for C20H15BrClN2O3: C, 52.14; H, 3.28; N, 9.12.
Found: C, 52.07; H, 3.31; N, 8.99.
E t h yl cis-6-Aza -7-b u t yl-2-{[(3-ch lor op h en yl)a m in o]-
ca r b on yla m in o}-5-oxa sp ir o[3.4]oct -6-en -2-ca r b oxyla t e
(17e) fr om 16b. As with 16a f 17a , compound 16b (120 mg,
0.47 mmol) and 3-chlorophenyl isocyanate (72 mg, 0.47 mmol)
gave compound 17e (184 mg, 0.45 mmol, 96%) as a solid: Mp
127 °C; FTIR (KBr) 1726, 1681 cm-1 1H NMR (300 MHz,
;
CDCl3) δ 7.75 (s, 1H), 7.39 (s, 1H), 7.21 (m, 1H), 7.10 (t, 1H,
J ) 8.0 Hz), 6.91 (m, 1H), 6.37 (s, 1H), 4.25 (q, 2H, J ) 7.1
Hz), 3.21 (s, 2H), 3.05 (d, 2H, J ) 14.1 Hz), 2.75 (d, 2H, J )
14.1 Hz), 2.37 (t, 2H, J ) 7.8 Hz), 1.53 (m, 2H), 1.37 (m, 2H),
1.28 (t, 3H, 7.1 Hz), 0.93 (t, 3H, 7.3 Hz); 13C NMR (75 MHz,
CDCl3) δ 173.8, 161.0, 154.5, 140.2, 134.4, 129.7, 122.6, 119.1,
117.1, 80.0, 61.8, 50.6, 48.9, 47.0, 28.4, 27.5, 22.3, 14.1, 13.6.
Eth yl cis-6-Aza -2-[(bu tyla m in o)ca r bon yla m in o]-5-oxa -
7-p h en ylsp ir o[3.4]oct-6-en -2-ca r boxyla te (17f) fr om 16c.
As with 16a f 17a , compound 16c (110 mg, 0.40 mmol) and
butyl isocyanate (39 mg, 0.40 mmol) gave compound 17f (146
mg, 0.39 mmol, 98%) as a solid: Mp 171-172 °C; FTIR (KBr)
1734, 1624 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.65-7.62 (m,
2H), 7.40-7.38 (m, 3H), 5.90 (s, 1H), 5.31 (s, br, 1H), 4.25 (q,
2H, J ) 7.0 Hz), 3.58 (s, 2H), 3.14-3.11 (m, 2H), 3.06 (d, 2H,
14.0 Hz), 2.82 (d, 2H, 14.0 Hz), 1.46-1.41 (m, 2H), 1.38-1.27
(m, 5H), 0.87 (t, 3H, J ) 7.3 Hz); 13C NMR (75 MHz, CDCl3)
δ 174.3, 157.6, 157.4, 130.2, 129.3, 128.7, 126.6, 81.3, 61.4, 50.7,
47.2, 46.6, 39.9, 32.3, 19.9, 14.1, 13.7. Anal. Calcd for
cis-2,4,9-Tr ia za -10-b u t yl-2-(3-ch lor op h en yl)-8-oxa d i-
sp ir o[4.1.4.1]d od ec-9-en e-1,3-d ion e (18e) fr om 17e. As
with 17a f 18a , compound 17e (100 mg, 0.24 mmol) and Na
(6.7 mg, 0.29 mmol) gave compound 18e (80 mg, 0.22 mmol,
1
91%) as a solid: Mp 143 °C; FTIR (KBr) 1778, 1726 cm-1; H
NMR (300 MHz, CDCl3) δ 7.48 (s, 1H), 7.40-7.33 (m, 3H), 7.07
(s, 1H), 3.34 (s, 2H), 3.07 (d, 2H, J ) 12.4 Hz), 2.94 (d, 2H,
J ) 12.4 Hz), 2.36 (t, 2H, J ) 7.4 Hz), 1.57 (m, 2H), 1.37 (m,
2H), 0.93 (t, 3H, 7.2 Hz); 13C NMR (75 MHz, CDCl3) δ 175.5,
160.6, 154.2, 134.6, 132.6, 129.9, 128.2, 126.0, 123.9, 77.9, 53.6,
48.1, 47.0, 28.3, 27.4, 22.3, 13.6. Anal. Calcd for C18H20
-
ClN3O3: C, 59.75; H, 5.57; N, 11.61. Found: C, 59.88; H, 5.61;
N, 11.47.
cis-2,4,9-Tr ia za -2-bu tyl-8-oxa -10-p h en yldisp ir o[4.1.4.1]-
d od ec-9-en e-1,3-d ion e (18f) fr om 17f. As with 17a f 18a ,
compound 17f (100 mg, 0.27 mmol) and Na (7.3 mg, 0.32 mmol)
gave compound 18f (79 mg, 0.24 mmol, 90%) as a solid: Mp
169-170 °C; FTIR (KBr) 1777, 1710 cm-1; 1H NMR (300 MHz,
CDCl3) δ 7.72-7.69 (m, 2H), 7.43-7.41 (m, 3H), 7.14 (s, 1H),
3.78 (s, 2H), 3.52 (t, 2H, J ) 7.2 Hz), 3.12 (d, 2H, J ) 14.0
Hz), 2.94 (d, 2H, J ) 14.0 Hz), 1.63 (m, 2H), 1.35 (m, 2H),
0.95 (t, 3H, J ) 7.3 Hz); 13C NMR (75 MHz, CDCl3) δ 177.1,
157.7, 156.2, 130.4, 129.0, 128.8, 126.7, 79.2, 53.4, 46.9, 45.8,
38.5, 30.1, 19.9, 13.6. Anal. Calcd for C18H21N3O3: C, 66.03;
H, 6.46; N, 12.83. Found: C, 65.91; H, 6.50; N, 12.69.
C
20H27N3O4: C, 64.32; H, 7.28; N, 11.25. Found: C, 64.40; H,
7.19; N, 11.16.
cis-2,4,9-Tr ia za -10-(4-br om op h en yl)-8-oxa -2-p h en yld i-
sp ir o[4.1.4.1]d od ec-9-en -1,3-d ion e (18a ) fr om 17a . To a
solution of compound 17a (100 mg, 0.21 mmol) and EtOH (10
mL) was added sodium (6 mg, 0.25mmol), and the reaction
mixture was stirred at room temperature for 2 h. EtOH was
removed under reduced pressure. Ethyl acetate and water
were added to the residue. Ethyl acetate layer was dried over
anhydrous MgSO4, concentrated, and recrystallized to give the
compound 18a (81 mg, 0.19 mmol, 94%) as a solid: Mp 250-
Ack n ow led gm en t. We are grateful to the National
Science Foundation for financial support of this re-
search. The 400 and 300 MHz NMR spectrometers used
in this study were funded in part by a grant from NSF
(Grant No. CHE-9808183).
251 °C; FTIR (KBr) 1767, 1717 cm-1 1H NMR (300 MHz,
;
MeOH d-4, acetone-d6) δ 7.59 (s. 4H), 7.43-7.34 (m, 6H), 3.75
(s, 2H), 3.03 (d, 2H, J ) 13.2 Hz), 2.92 (d, 2H, J ) 13.2 Hz);
13C NMR (75 MHz, DMSO-d6) δ 175.8, 157.0, 154.5, 132.2,
132.0, 128.8, 128.7, 128.6, 127.9, 126.8, 123.6, 79.3, 52.9, 46.7,
45.0. Anal. Calcd for C20H16BrN2O3: C, 56.35; H, 3.78; N, 9.85.
Found: C, 56.11; H, 3.72; N, 9.71.
cis-2,4,9-Tr ia za -10-bu tyl-8-oxa -2-p h en yld isp ir o-[4.1.4.1]-
d od ec-9-en -1,3-d ion e (18b) fr om 17b. As with 17a f 18a ,
compound 17b (100 mg, 0.26 mmol) and Na (7 mg, 0.32 mmol)
Su p p or tin g In for m a tion Ava ila ble: 1H NMR, 13C NMR,
and FTIR spectra for compounds 5, 14c, 16a , 16b, 16c, 17a ,
17c, 17d , and 17e as well as X-ray crystallographic data for
18d . This material is available free of charge via the Internet
at http://pubs.acs.org.
J O000152C