P.D. Woodgate et al. / Journal of Organometallic Chemistry 592 (1999) 180–193
189
(
6
4
(
5
2
C-8a,11a), 119.9 (C-8,12), 121.4 (C-3,17), 122.8 (C-
,14), 126.5 (C-7,13), 127.2 127.8, (C-Ph), 128.3 (C-
120.1 (C-8,12), 121.4 (C-3,17), 123.0, 126.6 (C-
4%,5%,6,14?), 126.6 (C-7,13), 127.8 (C-3%), 128.4 (C-
4a,15a), 128.8 (C-5,15), 129.8 (C-4,16), 131.2
a,15a), 128.7 (C-5,15), 129.9 (C-4,16), 131.1
+
C-8b,11a), 133.0 (C-1%) 151.6 (C-2a,17a). m/z (DEI )
(C-8b,11a), 141.9 (C-2%), 151.3 (C-2a,17a). m/z
+
53 (M, 14%), 538 (M−CH , 30), 496 (M−(CH ) C,
(DEI ) 459 (M, 29%), 351 (M−C
6
H
5
CH
H O, 100).
9
2
OH, 20),
3
3 3
), 482 (M−(CH ) CCH , 42), 476 (M−C H , 100).
336 (351−CH
. Compound
, 9), 302 (M−C11
3
3
3
2
6
5
+
2
15b: (Found:
M
459.2025,
C H BNO . Calc.: 45.2006). w
aromatic), 1247, 1140, 1056, 1029 cm
1624, 1599 (CꢁC
4
.7. Cis-N-methyl-1-(2-hydroxyethoxy)-bis-
30 26
3
max
−
1
(naphthyl)[2,1-c:1,2-h]-10-aza-1-borabicyclooctane (14)
(CꢀO). lB
2
4
3
.15. lH 2.75 (s, 3H, NCH ), 4.54, 4.92 (2d, J 13.8,
H, H-9,11), 4.64 (s, 2H, H-1%), 6.98 (m, 2H, H-
%,7%), 6.99 (m, 3H, H-4%,5%,6%), 7.26 (d, J 8.9, 1.9, 2H,
3
Amine 9 (0.20 g, 0.59 mmol), boric oxide (0.02 g, 0.3
mmol), and ethane-1,2-diol (0.02 g, 0.3 mmol) in ben-
zene (5 ml) were placed in a flask fitted with a Dean–
Stark water separator. The mixture was heated under
reflux for 12 h, then concentrated in vacuo. Flash
column chromatography on silica gel (dichloromethane;
dichloromethane–methanol, 10:1) afforded 14 (0.18 g,
H-3,17), 7.36 (td, J 7.4, 2H, H-6,14), 7.50 (td, J 7.6,
.2, 2H, H-7,13), 7.61 (d, J 8.3, 2H, H-8,12), 7.74 (d,
1
J 8.9, 2H, H-4,16), 7.81 (d, J 8.4, 2H, H-5,15). lC
4
8
3.2 NCH , 58.6 (C-9,11), 63.7 (C-1%), 108.1 (C-
a,11b), 120.3 (C-8,12, 121.7 (C-3,17), 123.1, 126.5,
3
(
C-4%,5%,6,14), 126.7 (C-7,13), 127.7 (C-3%), 128.6 (C-
4a,15a), 128.9 (C-5,15), 129.8 (C-4,16), 131.4 (C-
b,11a), 142.0 (C-2%), 152.0 (C-2a,17a). m/z 459 (M,
31%), 351 (M−C CH OH, 26), 336 (351-CH
), 302 (M−C H O, 100).
75%) as colourless rhomboids, m.p. 221–2°C. (Found:
+
M
459.1995, C H BNO . Calc.: 459.2006). w
3445
3
0
26
3
max
8
(
1
br, OH), 1625, 1560 (CꢁC aromatic), 1271, 1247, 1156,
−
1
6
H
5
2
,
3
098, 1045 cm
(CꢀO). lH 2.97 (s, 3H, NCH ), 3.67
3
6
11
9
(
s, 2H, H-2%), 3.81 (s, 2H, H-1%), 4.48, 4.60 (2d, J 14.8,
4
2
2
2
6
H, H-9,11), 7.17 (d, J 8.9, 2H, H-3,17), 7.33 (t, J 7.4,
H, H-6,14), 7.45 (t, J 6.7, 2H, H-7,13), 7.50 (d, J 8.4,
H, H-8,12), 7.72 (d, J 8.9, 2H, H-4,16), 7.78 (d, J 8.0,
4
1
.8. Cis-N-methyl-1-nonoxy-bis(naphthyl)[2,1-c:1,2-h]-
0-aza-1-borabicyclooctane (16)
H, H-5,15). lC 44.9 NCH , 56.9 (C-2%), 63.8 (C-1%),
3
Amine 9 (0.21 g, 0.51 mmol) and boric oxide (0.02 g,
.51 mmol) in benzene (5 ml) and nonan-1-ol (0.1 g,
.51 mmol) were placed in a flask fitted with a Dean–
4.1 (C-9,11), 107.2 (C-8a,11a), 120.2 (C-8,12), 121.3
0
0
(
C-3,17), 123.2 (C-6,14), 126.7 (C-7,13), 128.6 (C-
4
8
3
a,15a), 128.9 (C-5,15), 130.0 (C-4,16), 131.2 (C-
b,11a), 151.1 (C-2a, 17a). m/z (DEI ) 413 (M, 30%),
69 (M−C H O, 22), 352 (M−OCH H OH, 16), 212
Stark water separator. The mixture was heated under
reflux for 12 h, then concentrated in vacuo. Flash
column chromatography on silica gel (dichloromethane;
dichloromethane–methanol, 10:1) gave 16 (0.16 g, 64%)
+
2
4
2
2
(
100).
Amine 9 (0.22 g, 0.53 mmol) and boric oxide (0.03 g,
.32 mmol) in toluene (5 ml) and benzyl alcohol (0.07 g,
.53 mmol) were placed in a flask fitted with a Dean–
+
as a yellow oil. (Found: M 495.2955, C H BNO .
32
38
3
0
0
Calc.: 495.2945). wmax 1624, 1580 (CꢁC aromatic), 1248,
−1
1
157, 1097, 1042, 1029 cm
(CꢀO). lH 0.94 (t, J 7.2,
Stark water separator. The mixture was heated under
reflux for 12 h, then concentrated in vacuo. Chro-
matography of the oily residue on silica gel
3
H, H-9%), 1.14 (m, 12H, H-3%-8%), 1.14 (t, J 7.2, 2H,
H-2%), 2.89 (s, 3H, NCH ), 3.69 (t, J 6.6, 2H, H-1%),
3
4
2
2
2
2
.41, 4.54 (2d, br, J 14.0, 4H, H-9,11), 7.18 (d, J 7.2,
H, H-3,17), 7.27 (t, J 7.1, 2H, H-6,14), 7.41 (t, J 6.7,
H, H-7,13), 7.46 (d, J 8.2, 2H, H-8,12), 7.68 (d, J 8.9,
(
dichloromethane; dichloromethane–methanol, 10:1)
gave, in decreasing order of polarity, cis-N-methyl-1-
benzyloxy-bis(naphthyl)[2,1-c:1,2-h]-10-aza-1-bora-
bicyclooctane (15a) (0.17 g, 73%) as colourless plates,
m.p. 218–9°C (acetone), and trans-N-methyl-1-benzy-
loxy-bis(naphthyl)[2,1-c:1,2-h]-10-aza-1-borabicyclooc-
tane (15b) (0.04 g, 17%) as colourless plates, m.p.
H, H-4,16), 7.74 (d, J 8.0, 2H, H-5,15). l 14.1 (C-9%),
C
2.6 (C-8%), 26.0 (C-7%), 29.2 (C-6%), 29.3 (C-5%), 29.6
(
C-4%), 31.8 (C-3%), 32.2 (C-2%), 44.7 NCH , 56.8 (C-1%),
3
6
(
4
2.0 (C-9,11), 107.3 (C-8a,11a), 120.1 (C-8,12), 121.6
C-3,17), 123.0 (C-6,14), 126.6 (C-7,13), 128.5 (C-
a,15a), 128.9 (C-5,15), 129.8 (C-4,16), 131.3 (C-
160–1°C (acetone).
+
1
. Compound 15a: (Found: M 459.2014, C H -
30
26
8b,11a), 151.6 (C-2a,17a). m/z 495 (M, 30%), 351
(M−C H OH, 30), 338 (M−C H O, 100).
BNO . Calc.: 459.2006). w
1622, 1598 (CꢁC aro-
3
max
9
19
11
9
−
1
matic), 1264, 1244, 1082, 1052 cm (CꢀO). l 2.24.
Amine 9 (0.26 g, 0.75 mmol) and boric oxide (0.03 g,
0.38 mmol) in benzene (5 ml) and propan-2-ol (0.2 g,
3.3 mmol) were placed in a flask fitted with a Dean–
Stark water separator. The mixture was heated under
reflux for 12 h, then concentrated in vacuo. Chro-
matography on silica gel (dichloromethane; dichloro-
methane–methanol, 10:1) gave, in decreasing order of
B
lH 2.85 (s, 3H, NCH ), 4.35, 4.50 (2d, J 14.7, 4H,
3
H-9,11), 4.83 (s, 2H, H-1%) 7.10 (m, 2H, H-3%,7%),
,
7
.18 (m, 5H, H-3,17,4%,5%,6%), 7.27 (td, J 7.0, 1.9, 2H,
H-6,14), 7.38 (m, 4H, H-7,8,12,13), 7.66 (d, J 8.9,
H, H-4,16), 7.72 (d, J 8.0, 2H, H-5,15). lC 44.7
NCH , 56.7 (C-9,11), 64.1 (C-1%), 107.2 (C-8a,11b),
2
3