3772 J . Org. Chem., Vol. 61, No. 11, 1996
Połon´ski et al.
3.2 and 13.1 Hz, 2 H), 2.26 (m, 1 H), 2.04 (m, 2 H), 1.91 (m, 2
H), 1.70 (m, 5 H); 13C NMR (CDCl3) δ 46.9, 30.1, 28.9, 25.4,
19.8.
δ 212.6, 159.9 (d, J CF ) 246.4 Hz), 129.2, 127.9 (br), 123.8 (d,
J CF ) 3.0 Hz), 116.0 (d, J CF ) 23.1 Hz), 64.6 (br), 49.6, 37.9,
21.0, 20.2; 19F NMR (CDCl3) δ -114.6 (br s, 1 F), -108.4 (br s,
1 F); UV (cyclohexane-dioxane, 4:1) λmax 416 nm (ꢀ 88). Anal.
Calcd for C22H22N2O2F2 (384): C, 68.74; H, 5.77; N, 7.29.
Found: C, 68.60; H, 5.85; N, 7.22.
N -Nit r oso-2,4-d ip h e n yl-3-a za b icyclo[3.3.1]n on a n -9-
on e (1b). To a solution of amine 1a (1.45 g, 5 mmol) in
chloroform (10 mL) were added concd hydrochloric acid (1.5
mL) and water (1.5 mL), and while stirring, solid NaNO2 (0.84
g, 12 mmol) was added in portions during 0.5 h. The stirring
was continued for another 0.5 h. The organic layer was
washed with water and saturated NaHCO3 and dried over
MgSO4. After evaporation of the chloroform, the residue was
crystallized from toluene-heptane: yield 1.22 g (76%); mp
168-169 °C dec; 1H NMR (CDCl3) δ 7.45-7.25 (m, 10 H), 5.55
(br s, 2 H), 2.90 (m, 2 H), 2.03 (m, 1 H), 1.68 (m, 4 H), 1.38 (m,
1 H); 13C NMR (CDCl3) δ 212.9, 137.7 (br), 128.8, 127.4, 125.6
(br), 66.9 (br), 51.3, 29.9, 18.2; UV (cyclohexane) λmax 410 nm
(ꢀ 87). Anal. Calcd for C20H20N2O2 (320): C, 74.98; H, 6.29;
N, 8.74. Found: C, 74.65; H, 6.39; N, 8.63.
N-Nit r oso-1,5-d im et h yl-2,4-b is(2,6-d iflu or op h en yl)-3-
a za bicyclo[3.3.1]n on a n -9-on e (8b) was obtained from amine
8a in a manner similar to that of compound 1b: mp 181 °C
dec (from toluene); 1H NMR (CDCl3) δ 7.32 (m, 2 H), 6.97 (m,
4 H), 5.05 br s, 2 H), 2.17 (m, 2 H), 1.60 (m, 3 H), 1.03 (s, 3 H);
13C NMR (CDCl3) δ 213.4, 129.5 (br), 112.1 (br), 111.5 (dd, J CF
) 3.3 and 24.5 Hz), 63.2 (br), 50.8, 38.6, 20.4, 18.5 (t, J CF
)
13.0 Hz); 19F NMR (CDCl3, 5 °C) δ -103.6 (s, 1 F), -110.3 (s,
2 F), -111.4 (s, 1 F); UV (cyclohexane-dioxane, 4:1) λmax 412
(ꢀ 94). Anal. Calcd for C22H20N2O2F4 (421): C, 62.79; H, 4.79;
N, 6.66. Found: C, 62.84; H, 4.70; N, 6.70.
N-Nitr oso-2,4-d ip h en yl-3-a za bicyclo[3.3.1]n on a n e (9b)
was obtained from amine 9a in a similar manner to that of
compound 1b: mp 166-167 °C (from MeOH); 1H NMR (CDCl3)
δ7.60-7.10 (complex m, 10 H), 5.71 (br s, 1 H), 4.95 (br s, 1
H), 2.52 (m, 1 H), 2.43 (m, 1 H), 2.05 (m, 2 H), 1.62 (m 1 H),
1.53 (m, 1 H), 1.37 (m, 1 H), 1.27 (m, 2 H), 1.12 (m, 1 H); 13C
NMR (CDCl3) δ 141.4, 139.8, 128.5, 128.3, 127.0, 126.8, 126.1,
124.1, 68.7, 64.1, 34.6, 33.9, 32.1, 31.6, 31.1, 27.1, 26.3, 18.8;
UV (cyclohexane) λmax 405 nm (ꢀ 88). Anal. Calcd for
N-Nit r oso-1-m et h yl-2,4-d ip h en yl-3-a za b icyclo[3.3.1]-
n on a n -9-on e (2b) was obtained from amine 2a in a manner
similar to that of compound 1b: mp 162-163 °C (from MeOH);
1H NMR (CDCl3) δ 7.55-7.15 (complex m, 10 H), 5.32 (br s, 1
H), 5.08 (br s, 1 H), 2.98 (m, 1 H), 2.30 (m, 1 H), 1.94 (m, 1 H),
1.67 (m, 2 H), 1.48 (m, 2 H), 1.11 (s, 3 H); 13C NMR (CDCl3) δ
213.8, 137.2, 136.7, 128.7, 128.4, 128.0, 127.2, 125.1 (br), 74.5
(br), 65.8 (br), 50.9, 49.5, 37.3, 30.3, 21.5, 19.2; UV (cyclohex-
ane) λmax 413 nm (ꢀ 78). Anal. Calcd for C21H22N2O2 (334):
C, 75.42; H, 6.63; N, 8.38. Found: C, 75.17; H, 6.66; N, 8.43.
N-Nitr oso-1,5-dim eth yl-2,4-diph en yl-3-azabicyclo[3.3.1]-
n on a n -9-on e (3b) was obtained from amine 3a in a manner
similar to that of compound 1b: mp 174-175 °C dec (from
C
20H22N2O (306): C, 78.40; H, 7.24; N, 9.14. Found: C, 78.31;
H, 7.28; N, 9.24.
N-Nit r oso-1-m et h yl-2,4-d ip h en yl-3-a za b icyclo[3.3.1]-
n on a n e (10b) was obtained from amine 10a in a similar
manner to that of compound 1b: mp 139 °C (from MeOH); 1H
NMR (CDCl3) δ 7.60-7.05 (complex m, 10 H), 5.67 (br s, 0.7
H), 5.07 (br s, 0.7 H), 4.88 (br s, 0.7 H), 4.49 (br s, 0.3 H), 2.58
(m, 1 H), 1.84 (m, 3 H), 1.70-1.10 (comlex m, 5 H), 1.07 (s, 0.9
H), 1.06 (s, 2.1 H); 13C NMR (CDCl3) δ 139.2 (br), 129.0, 128.1,
127.4, 126.6 (br), 125.9, 124.1, 75.7, 70.7 (br), 68.1 (br), 63.5,
39.7, 34.4, 34.0, 33.3, 30.2, 26.7, 25.9, 19.6; UV (cyclohexane)
1
toluene); H NMR (CDCl3) δ 7.42 (m, 10 H), 4.89 (br s, 2 H),
2.65 (m, 1 H), 1.88 (m, 2 H), 1.54 (m, 3 H), 1.15 (s, 6 H); 13C
NMR (CDCl3) δ 214.3, 136.4, 128.2, 127.5, 73.5 (br), 48.9, 37.5,
21.9, 19.9; UV (cyclohexane) λmax 417 nm (ꢀ 85). Anal. Calcd
for C22H22N2O2 (348): C, 75.83; H, 6.94; N, 8.04. Found: C,
75.86; H, 6.99; N, 8.11.
N-Nit r oso-1,5-d im et h yl-2,4-b is(3-m et h oxyp h en yl)-3-
a za bicyclo[3.3.1]n on a n -9-on e (4b) was obtained from amine
4a in a manner similar to that of compound 1b: mp 167 °C
λ
max 413 nm (ꢀ 78). Anal. Calcd for C21H24N2O (320): C, 78.72;
1
H, 7.55, N, 8.74. Found: C, 78.75; H, 7.72; N, 8.77.
dec; H NMR (CDCl3) δ 7.36 (t, J ) 7.8 Hz, 2 H), 7.08 (m, 2
H), 7.01 (m, 2 H), 6.91 (dd, J ) 2.0 and 7.8 Hz, 2 H), 4.88 (br
s, 2 H), 3.87 (s, 6 H), 2.63 (m, 1 H), 1.96 (m, 2 H), 1.62 (m, 1
H), 1.51 (m, 2 H), 1.19 (s, 6 H); 13C NMR (CDCl3) δ 214.3, 159.4,
138.0, 129.2, 120.0, 114.2, 112.3, 73.4 (br), 55.1, 48.9, 37.6, 22.1,
19.9; UV (cyclohexane-dioxane, 4:1) λmax 412 nm (ꢀ 78). Anal.
Calcd for C24H28N2O4 (408): C, 70.57; H, 6.91; N, 6.86.
Found: C, 70.55; H, 6.97; N, 6.90.
N-Nitr oso-3-a za bicyclo[3.3.1]n on a n e (11b) was obtained
from amine 11a by N-nitrosation with HNO2: mp 164-166
°C (from hexane); 1H NMR (CDCl3) δ 4.92 (m, 1 H), 4.78 (m, 1
H), 3.95 (m, 1 H), 3.93 (m, 1 H), 2.74 (m, 1 H), 2.18 (m, 1 H),
2.08 (m, 1 H), 1.92 (m, 1 H), 1.86 (m, 2 H), 1.80-1.55 (complex
m, 3 H), 1.40 (m, 2 H); 13C NMR (CDCl3) δ 55.6, 44.7, 32.3,
30.9, 30.0, 28.1, 27.2, 18.5; UV (cyclohexane) λmax 365 nm (ꢀ
135). Anal. Calcd for C8H14N2O (154): C, 62.31; H, 9.15; N,
18.17. Found: C, 62.03; H, 9.41; N, 17.91.
N -N it r o s o -1,5-d im e t h y l-2,4-b is (4-flu o r o p h e n y l)-3-
a za bicyclo[3.3.1]n on a n -9-on e (5b) was obtained from amine
5a in a manner similar to that of compound 1b: mp 189 °C
dec (from toluene); 1H NMR (CDCl3) δ 7.39 (m, 4 H), 7.12 (t, J
) 8.6 Hz, 4 H), 4.82 (br s, 2 H), 2.54 (m, 1 H), 1.86 (m, 2 H),
1.62 (m, 1 H), 1.52 (m, 2 H), 1.11 (s, 6 H); 13C NMR (CDCl3) δ
213.9, 162.1 (d, J CF ) 246.1 Hz), 132.1, 129.1 (d, J CF ) 7.8
Hz), 115.3 (d, J CF ) 22.2 Hz), 72.9 (br), 49.0, 37.4, 21.8, 20.1;
19F NMR (CDCl3) δ -114.7; UV (cyclohexane-dioxane, 4:1)
λmax 414 nm (ꢀ 90). Anal. Calcd for C22H22N2O2F2 (384): C,
68.74; H, 5.77; N, 7.29. Found: C, 68.85; H, 5.70; N, 7.13.
N -N it r o s o -1,5-d im e t h y l-2,4-b is (3-flu o r o p h e n y l)-3-
a za bicyclo[3.3.1]n on a n -9-on e (6b) was obtained from amine
6a in a manner similar to that of compound 1b: mp 180 °C
dec (from toluene); 1H NMR (CDCl3) δ 7.43 (m, 2 H), 7.24 (m,
2 H), 7.16 (m, 2 H), 7.09 (t, J ) 8.3 Hz, 2 H), 4.84 (br s, 2 H),
2.57 (m, 1 H), 1.93 (m, 2 H), 1.70 (m, 1 H), 1.67 (m, 2 H), 1.17
(s, 6 H); 13C NMR (CDCl3) δ 213.6, 162.7 (d, J CF ) 246.0 Hz),
138.8 (d, J CF ) 3.0 Hz), 129.9 (d, J CF ) 7.9 Hz), 123.4, 114.8
(d, J CF ) 21.2 Hz), 73.0 (br), 48.9, 37.5, 21.9, 20.1; 19F NMR
(CDCl3) δ -112.8 (br); UV (cyclohexane-dioxane, 4:1) λmax 414
(ꢀ 88). Anal. Calcd for C22H22N2O2F2 (384): C, 68.74; H, 5.77;
N, 7.29. Found; C, 69.02; H, 5.82; N, 7.21.
X-r a y Diffr a ction An a lysis. Crystal data for C22H24N2O2
(3b): orthorhombic, space group Pnma, a ) 8.043(2) Å, b )
20.900(4) Å, c ) 11.094(2) Å, V ) 1864.9(7) Å3, Z ) 4, Dcalcd
)
1.241 g cm-3, λ(Cu KR1) ) 1.54178 Å, T ) 293 K, R ) 0.036
for 1643 independent reflections with I > 2σ(I). Crystal data
for C22H20F4N2O2 (8b): orthorhombic, P212121, a ) 7.873(2) Å,
b ) 11.391(2) Å, c ) 21.706(4) Å, V ) 1946.6(7) Å3, Z ) 4,
Dcalcd ) 1.434 g cm-3, λ(Cu KR1) ) 1.54178 Å, T ) 293 K, R )
0.032 for 3322 independent reflections with I > 2σ(I).
Ack n ow led gm en t. We we wish to thank to Dr. P.
Sowin˜ski for many helpful discussions, Mrs. J . Woszczyk
and Mr. W. Ciesielski (PAN Ło´dz´) for variable temper-
ature NMR measurements.
Su p p or tin g In for m a tion Ava ila ble: The ORTEP draw-
1
ing of the X-ray structure of 3b, the variable temperature H
and 19F NMR spectra of 4b and 7b, respectively, and UV-vis
spectra of 3b and 11b (5 pages). This material is contained
in libraries on microfiche, immediately follows this article in
the microfilm version of the journal, and can be ordered from
ACS. Ordering information is given on any current masthead
page.
N -N it r o s o -1,5-d im e t h y l-2,4-b is (2-flu o r o p h e n y l)-3-
a za bicyclo[3.3.1]n on a n -9-on e (7b) was obtained from amine
7a in a manner similar to that of compound 1b: mp 182 °C
1
dec; H NMR (CDCl3) δ 7.62 (br, 2 H), 7.36 (m, 2 H), 7.20 (m,
4 H), 5.17 (br s, 2 H), 2.77 (m, 1 H), 2.11 (m, 2 H), 1.75 (m, 1
H), 1.61 (m, 2 H), 1.10 (d, J HF ) 3.4 Hz, 6 H); 13C NMR (CDCl3)
J O9600159