6
544 J . Org. Chem., Vol. 61, No. 19, 1996
Ziessel et al.
g of a clear brown crystalline material, 87%: mp 168/9 °C; IR
P r ep a r a tion of 4-(1,3-bu ta d iyn yl)p yr id in e (9b): 4-[4-
(triethylsilyl)-1,3-butadiynyl]pyridine (1.000 g, 4.1 mmol).
-1
(
(
CCl
4
, cm ) 2960 (s), 2905 (s), 2870 (s), 2100 (s), 1445 (s), 1425
1
s), 1040 (s), 1015 (s); H NMR (CDCl
3
) δ 0.71 (q, 6H, J ) 8.0
Chromatographed on flash silica gel (hexane/CH
10 to 20) to give 0.410 g of a colorless liquid (78%): R
(CH Cl /hexane 1/1, silica TLC sheet treated with triethy-
lamine); IR (CHCl
NMR (CD Cl ) δ 2.69 (s, 1H), 7.36 (d, 2H, J ) 4.5 Hz), 8.59 (d,
2H, J ) 4.5 Hz); C{ H} NMR (CD
126.6, 129.3, 150.3; EI/MS m/z (%) 127 (M , 100); Anal. Calcd
for C N: C, 85.02; H, 3.96; N, 11.02. Found: C, 84.87; H,
.95; N, 10.94.
-(1,3-B u t a d i y n y l)-5,5′-d i m e t h y l-2,2′-b i p y r i d i n e
11b): 6-[4-(triethylsilyl)-1,3-butadiyne]-5,5′-dimethyl-2,2′-bi-
pyridine (1.000 g, 2.88 mmol). A 0.602 g amount of 11b was
obtained, 90%: mp 87 °C dec; R 0.30 (CH Cl , silica); IR (KBr,
cm ) 3167 (s), 2965 (s), 2053 (s), 1547 (s), 1491 (s), 1439 (vs),
2
Cl
2
90 to 80/
Hz), 1.03 (t, 9H, J ) 8.0 Hz), 7.51 (dd, 1H, J ) 7.6, 0.9 Hz);
f
) 0.34
1
3
7
{
1
(
C
.78 (t, 1H, J ) 7.6 Hz), 8.43 (dd, 1H, J ) 7.6, 0.9 Hz); C-
2
2
1
-1
1
H} NMR (CDCl
3
) δ 4.1, 7.3, 73.8, 74.8, 88.4, 90.3, 121.4,
3
, cm ) 3290 (s), 2970 (br), 1585 (vs); H
+
28.5, 137.1, 141.2, 155.7; EI/MS m/z (%) 480 (M , 85), 451
2
2
+
+
13
1
M
- C
2
H
5
, 100), 422 (M - 2C
2
H
5
, 15). Anal. Calcd for
2 2
Cl ) δ 67.4, 72.6, 73.8, 77.4,
+
30 36 2 2
H N Si : C, 74.94; H, 7.55; N, 5.83. Found: C, 74.77; H,
7
.32; N, 5.76.
,6′-Bis(1,3-n on a d iyn yl)-2,2′-bip yr id in e (13b): 6,6′-di-
ethynyl-2,2′-bipyridine (0.200 g, 0.98 mmol), CuCl (0.010 g,
.1 mmol), hydroxylamine hydrochloride (0.036 g, 0.52 mmol),
n-propylamine (1.5 mL), 1-iodohept-1-yne (0.544 g, 2.45 mmol).
Chromatographed on flash silica gel (hexane/CH Cl 30/70) to
give 0.326 g of a white crystalline compound, 85%: mp 162/3
9 5
H
3
6
6
(
0
f
2
2
2
2
-
1
1
-
1
1262 (s); H NMR (CD
1H), 7.62 (dd, 1H, J ) 8.1, 0.6 Hz), 7.65 (d, 1H, J ) 8.2 Hz),
.27 (d, 1H, J ) 7.8 Hz), 8.30 (d, 1H, J ) 7.8 Hz), 8.45 (d, 1H,
2 2
Cl ) δ 2.37 (s, 3H), 2.48 (s, 3H), 2.69 (s,
°
2
(
2
C; R
930 (s), 2240 (s), 1555 (br), 1435 (s), 1150 (w); H NMR
CDCl ), δ 0.92 (t, 3H, J ) 6.8 Hz), 1.26-1.64 (m, 6H), 2.38 (t,
H, J ) 6.7 Hz), 7.49 (dd, 1H, J ) 7.7, 1.0 Hz), 7.76 (t, 1H, J
f 2 2 4
0.65 (hexane/CH Cl 50/50); IR (CCl , cm ) 2960 (s),
1
8
3
1
3
1
J ) 0.6 Hz). C{ H} NMR (CD
73.8, 75.8, 120.6, 121.3, 134.2, 137.7, 138.1, 138.5, 140.4, 149.9,
52.9, 154.9; FAB (m-NBA) m/z (%) 233 ([M + H] , 100). Anal.
Calcd for C16 : C, 82.73; H, 5.21; N, 12.06. Found: C,
2 2
Cl ) δ 18.4, 19.1, 67.8, 73.0,
1
3
1
)
3
7.7 Hz), 8.42 (dd, 1H, J ) 7.7, 1.0 Hz); C{ H} NMR (CDCl )
+
+
1
δ 13.9, 19.5, 22.1, 27.8, 30.9, 84.8, 73.7, 74.1, 86.1, 121.0, 128.2,
+
+
12 2
H N
1
CH
3
97.0, 141.7, 155.7; EI/MS m/z (%) 392 (M , 100), 377 (M
-
+
+
82.51; H, 5.00; N, 11.83.
6,6′-Bis(1,3-bu ta d iyn yl)-2,2′-bip yr id in e (13c): 6,6′-bis-
4-(triethylsilyl)-1,3-butadiynyl]-2,2′-bipyridine (0.500 g, 1.04
mmol). The pure product (0.248 g) changed color very rapidly
from white to grey and must be used soon after its isolation,
3
, 25), 363 (M - CH
2
CH
3
, 10), 349 (M - (CH
2
)
2
CH
3
, 8),
+
+
35 (M - (CH
2
)
3
CH
3
, 6), 321 (M - (CH
2
4
CH
3
, 6). Anal.
[
Calcd for C28
5.49; H, 7.02; N, 7.03.
,4′-Bis[4-(t r ie t h ylsilyl)-1,3-b u t a d iyn yl]-2,2′-b ip yr i-
28 2
H N Si: C, 85.67; H, 7.19; N, 7.14. Found: C,
8
4
9
8%: mp 130 °C dec; R
f
0.65 (CH
cm ) 3244 (s), 2059 (w), 1561 (s), 1436 (s); H NMR (DMSO-
) δ 3.17 (s, 2H), 7.80 (d, 2H, J ) 7.5 Hz), 8.04 (t, 2H, J ) 7.5
2 2
Cl /hexane 7/3); IR (KBr,
d in e (15a ): 4,4′-diethynyl-2,2′-bipyridine (0.300 g, 1.46 mmol),
CuCl (0.022 g, 0.22 mmol), hydroxylamine hydrochloride (0.056
g, 0.8 mmol), n-propylamine (2.5 mL), 1-bromo-2-(triethylsilyl)-
acetylene (0.490 g, 2.23 mmol). Chromatographed on flash
silica gel (hexane/ethylacetate 95/5) to give 0.567 g of a yellow
-
1
1
d
6
Hz), 8.40 (d, 2H, J ) 7.5 Hz). Its very poor solubility in
common solvents prevented the obtention of a C NMR
spectrum. EI/MS m/z (%) 252 (M , 100). Anal. Calcd for
1
3
+
-1
4
crystalline powder, 80%: mp 63/4 °C; IR (CCl , cm ) 2957 (s),
C
3
18
H
8
N
2
: C, 85.70; H, 3.19; N, 11.10. Found: C, 85.52; H,
.01; N, 10.97.
,4′-Bis(1,3-bu ta d iyn yl)-2,2′-bip yr id in e (15b): 4,4′-bis-
4-(triethylsilyl)-1,3-butadiynyl]-2,2′ bipyridine (0.480 g, 1
1
2
3
872 (s), 2100 (s), 1581 (br), 1452 (s), 1358 (s); H NMR (CDCl )
δ 0.65 (q, 6H, J ) 8.0 Hz), 1.03 (t, 9H, J ) 8.0 Hz), 7.34 (dd,
4
1
)
9
9
3
H, J ) 5.0, 1.6 Hz), 8.45 (d, 1H, J ) 1.6 Hz), 8.61 (d, 1H, J
[
1
3
1
3
5.0 Hz). C{ H} NMR (CDCl ) δ 4.1, 7.3, 73.0, 78.6, 88.0,
mmol). The pure product (0.177 g) changed color very rapidly
from white to grey and must be used soon after its isolation,
+
1.6, 123.9, 126.2, 130.8, 149.2, 155.4; EI/MS m/z (%) 180 (M ,
+
+
+
0), 451 (M - C
2
H
5
, 100), 422 (M - 2C
2
H
5
, 50), 403 (M
, 18). Anal. Calcd for C30
: C, 74.94; H, 7.55; N, 5.83. Found: C, 74.82; H, 7.48; N,
.74.
′-[4-(Tr iet h ylsilyl)-1,3-b u t a d iyn yl]-2,2′:6′,2′′-t er p yr i-
-
-
1
7
(
0%: mp 140 °C dec; IR (KBr, cm ) 3196 (s), 2059 (m), 1587
+
C
2
H
5
, 20), 374 (M - 4C
2
H
5
36 2
H N -
1
s), 1457 (m), 1359 (m); H NMR (THF-d
8
) δ 2.73 (s, 2H), 7.56
Si
5
2
13
(
{
d, 1H, J ) 5.0 Hz), 8.61 (s, 1H) 8.75 (d, 1H, J ) 5.0 Hz); C-
1
H} NMR (THF-d
51.8, 157.6; EI/MS m/z (%) 252 (M , 100). Anal. Calcd for
: C, 85.70; H, 3.19; N, 11.10. Found: C, 85.61; H,
.02; N, 10.98.
′-(1,3-Bu ta d iyn yl)-2,2′:6′,2′′-ter p yr id in e (17b): 4′-[4-
triethylsilyl)-1,3-butadiynyl]-2,2′:6′,2′′-terpyridine (0.300 g, 0.7
mmol), 93%: R 0.60 (alumina, CH Cl /CH OH 99/1); mp 110
C dec; IR (CHCl , cm ) 3210 (s), 2925 (br), 2065 (w), 1584
s), 1565 (s), 1463 (br), 1388 (br); H NMR (CDCl
H) 7.36 (ddd, 2H, J ) 7.5, 4.8, 1.0 Hz), 7.87 (td, 2H, J ) 7.7,
J ) 1.7 Hz), 8.55 (s, 2H), 8.58 (d, 2H, J ) 8.0 Hz), 8.70 (d, 2H,
8
) δ 73.7, 77.6, 79.4, 125.4, 128.5, 132.3,
4
+
1
d in e (17a ): 4′-ethynyl-2,2′:6′,2′′-terpyridine (1.340 g, 5.21
mmol), CuCl (0.060 g, 0.606 mmol), hydroxylamine hydrochlo-
ride (0.220 g, 3.16 mmol), n-propylamine (20mL), 1-bromo-2-
18 8 2
C H N
3
4
(
triethylsilyl)acetylene (2.200 g, 10 mmol). Chromatographed
on alumina (CH Cl /hexane 40/60) to give 1.100 g of a white
crystalline powder, 54%: mp 65/6 °C; R 0.74 (alumina, CH
, cm ) 2959 (s), 2876 (s), 2102 (s), 1583 (br),
(
2
2
f
2
2
3
f
2
-
-1
°
(
1
3
-
1
Cl
2
); IR (CHCl
3
1
3
) δ 2.58 (s,
1
1
467 (s), 1391 (s); H NMR (CD Cl ) δ 0.72 (q, 6H, J ) 8.0
2 2
Hz), 1.07 (t, 9H, J ) 8.0 Hz), 7.34 (ddd, 2H, J ) 7.5, 4.8, 1.0
Hz), 7.84 (td, 2H, J ) 7.7, 1.7 Hz), 8.51 (s, 2H), 8.56 (d, 2H, J
13
1
J ) 4.7 Hz); C{ H} NMR (DMSO-d
20.9, 121.2, 122.7, 124.9, 130.4, 137.6, 153.9, 155.5; FAB (m-
NBA) m/z (%) 282 ([M + H] , 100). Anal. Calcd for C19
6
) δ 64.9, 72.1, 78.6, 99.9,
1
3
1
)
8.0 Hz), 8.69 (d, 2H, J ) 4.8 Hz); C{ H} NMR (CD
2
Cl
2
) δ
+
1
4
1
1
.6, 7.6, 74.1, 78.3, 88.6, 91.8, 121.4, 123.7, 124.6, 131.8, 137.2,
+
11 3
H N :
49.6, 155.6, 156.1; FAB+ (m-NBA) m/z (%) 396 ([M + H] ,
+
C, 81.12; H, 3.94; N, 14.94. Found: C, 81.03; H, 3.72; N, 14.73.
P r ep a r a tion of th e Tr ieth ylsilyl P r otected Tr iyn e
Der iva tives 10, 12, 14, 19 (Ch a r ts 2 a n d 3). 4-[6-(Tr ieth -
ylsilyl)-1,3,5-h exa tr iyn yl]p yr id in e (10). 4-(1,3-Butadiyne)-
pyridine (0.400 g, 3.15 mmol) was dissolved in THF (40 mL).
After addition of CuCl (0.040 g, 0.4 mmol) and hydroxylamine
hydrochloride (0.080 g, 1.15 mmol), n-propylamine (4 mL) was
slowly added via a syringe. After a 5 min stirring, 1-bromo-
2-(triethylsilyl)acetylene (1.040 g, 4.74 mmol) in THF (5 mL)
was added dropwise. After a 4.5 h stirring, the reaction
2 5 3 25 3
00), 281 ([M - Si(C H ) + H], 15). Anal. Calcd for C25H N -
Si: C, 75.91; H, 6.37; N, 10.62. Found: C, 75.77; H, 6.09; N,
1
0.48.
P r ep a r a tion of th e Diyn e Der iva tives 9b, 11b, 13c, 15b,
7b (Ch a r t 2 a n d 3). Gen er a l P r oced u r e. To a solution
1
of the (triethylsilyl)-1,3-butadiyne derivatives (1.000 g scale)
in CH OH/CH Cl 4/1, an aqueous solution of NaOH (5 M, 4
mL) was added. After a 15 min of stirring, the organic product
was extracted with CH Cl
(3 × 75 mL), and the organic layer
was dried over MgSO . After filtration and evaporation of the
3
2
2
2
2
4
mixture was quenched with H
product extracted with CH Cl
(3 × 50 mL). The organic layer
was dried over MgSO . After filtration and evaporation of the
solvent, the crude material was chromatographed on flash
silica gel (CH Cl ) to give 0.240 g of a yellowish liquid, 29%:
0.42 (CH Cl ); IR (CCl
H NMR (CD Cl ) δ 0.63 (q, 6H, J ) 7.9 Hz), 0.98 (t, 9H, J )
7.9 Hz), 7.28 (d, 2H, J ) 4.7 Hz), 8.54 (d, 2H, J ) 4.7 Hz);
2
O (25 mL) and the organic
solvent, the crude material was chromatographed on flash
silica gel to give the analytically pure derivative 9b in good
yield. For other compounds after stirring for 2 h, the organic
solvent was evaporated by rotary evaporation resulting in the
precipitation of a white product. The pure compound was
2
2
4
2
2
-
1
R
f
2
2
4
, cm ) 2930 (br), 2110 (s), 1590 (vs);
1
filtered and washed with cold CH
3 × 50 mL) and dried under vacuum leading to the analyti-
cally pure derivative in fair yield.
3
OH (2 × 50 mL) and ether
2
2
(
1
3
1
2 2
C{ H} NMR (CD Cl ) δ 4.4, 7.5, 60.0, 69.0, 73.8, 78.2, 88.6,