4
840 J . Org. Chem., Vol. 62, No. 14, 1997
Pr e´ v oˆ t e´ et al.
1
3C NMR δ 16.0 (d, J ) 7), 32.0 (d, J ) 10), 32.9 (d, J ) 14),
114.7, 117.8, 121.4 (d, J ) 4), 121.6 (d, J ) 5), 128.0, 128.3,
130.3, 130.4, 132.2, 137.1, 137.2 (d, J ) 11), 138.2, 138.3, 142.7,
143.6, 151.0 (d, J ) 7), 151.2 (d, J ) 9), 166.6, 167.5; IR (KBr)
6
1
3.4 (d, J ) 6), 121.5 (d, J ) 3), 127.6, 128.1, 132.0, 132.5,
36.8 (d, J ) 15), 138-140 (m), 150.7 (d, J ) 7), 151.2 (m).
-
1
Anal. Calcd for C1896
N, 11.24. Found: C, 48.17; H, 5.14; N, 11.07.
H
2472
N
378
O
477
P
190
S
94: C, 48.36, H, 5.29;
114 18 15 4 4
1663 cm (νCdO). Anal. Calcd for C108H N O P S : C,
60.15; H, 5.33; N, 11.69. Found: C, 59.97; H, 5.27; N, 11.60.
Gen er a l P r oced u r e for th e Syn th esis of Am in op h os-
Gen er a l P r oced u r e for th e Syn th esis of P h osp h on a te-
p h ite-Ter m in a ted Den d r im er s 10-[G
solution of 0.120 g of dendrimer 9-[G ] (n ) 1, 0.075 mmol; n
5, 0.0035 mmol) in THF (10 mL) were added chlorodieth-
1
] a n d 10-[G
5
]. To a
Ter m in a ted Den d r im er s 14-[G
1
]-14-[G
5
]. To 0.200 g of
n
dendrimer 1-[G ] (n ) 1, 0.140 mmol; n ) 2, 0.058 mmol; n )
n
)
3, 0.027 mmol; n ) 4, 0.013 mmol; n ) 5, 0.0064 mmol) were
added triethylamine (n ) 1, 30 µL; n ) 2, 50 µL; n ) 3, 50 µL;
n ) 4, 140 µL; n ) 5, 140 µL) and diethyl phosphite (the
ylphosphine (n ) 1, 130 µL, 0.90 mmol; n ) 5, 98 µL, 0.677
mmol) and triethylamine (n ) 1, 126 µL, 0.90 mmol; n ) 5,
1
00 µL, 0.677 mmol). The resulting mixture was stirred for 2
n
quantity necessary to dissolve 1-[G ]: n ) 1, 0.6 mL, n ) 2,
h at room temperature and then filtered and evaporated to
dryness to give a white powder, very sensitive to oxidation.
1.0 mL; n ) 3, 1.0 mL; n ) 4, 2.9 mL; n ) 5, 2.9 mL). The
mixture was stirred overnight at room temperature and then
evaporated under vacuum to give an oil. Addition of ether/
pentane precipitated this oil. The resulting powder was
3
1
1
1
0-[G ]: white powder; 40% yield (0.070 g); P NMR δ 52.5,
1
6
1
(
5
1
2.8, 139.2; H NMR δ 1.22 (t, J ) 7.0, 36H), 2.93 (d, J ) 1.0,
8H), 3.33 (d, J ) 10.4, 9H), 3.71-3.85 (m, 24H), 7.15-7.77
washed with acetonitrile.
1
3
31
m, 45H); C NMR δ 16.7 (d, J ) 6), 28.4, 32.9 (d, J ) 13),
14-[G ]: white powder; 27% yield (0.085 g); P NMR δ 21.3
1
7
7
1
9.7 (d, J ) 17), 121.4 (d, J ) 4), 126.9, 128.3, 132.5, 132.6,
(d, J PP ) 3.9, P(O)), 51.8 (s, P
0
), 62.0 (t, J PP ) 3.9, P
1
); H
33.3 (d, J ) 28), 138.2 (d, J ) 12), 149.9 (d, J ) 7), 150.9 (d,
NMR δ 1.20 (m, 36H), 3.30 (d, J ) 10.3, 9H), 3.92 (m, 24H),
1
3
J ) 8). Anal. Calcd for C96
H
132
N
18
O
21
P
10
S
4
: C, 49.87; H, 5.75;
4.90 (s, 6H), 4.93 (d, J ) 11.5, 6H), 7.15-7.73 (m, 39H);
C
N, 10.90. Found: C, 49.73; H, 5.71; N, 10.72.
NMR δ 16.2 (d, J ) 4), 32.7 (d, J ) 13), 63.0 (d, J ) 10), 63.2
(d, J ) 8), 69.8 (d, J ) 160), 121.0, 121.3, 128.2, 132.5, 133.8,
138.2 (d, J ) 12), 150.0 (d, J ) 7), 150.9 (d, J ) 6); IR (KBr)
1
0-[G
5
]: white powder; 64% yield (0.102 g); 31P NMR δ 62.6,
1
6
2
7
1
1
1
2.7, 138.6; H NMR δ 1.15-1.27 (m, 576H), 2.85 (d, J ) 1.87,
-1
88H), 3.25 (d, J ) 11.6, 279H), 3.70-3.86 (m, 384H), 7.11-
3270 cm (νOH). Anal. Calcd for C90
120 6 33 10 4
H N O P S : C, 48.00;
1
3
.60 (m, 945H); C NMR δ 16.7 (d, J ) 5), 28.4, 32.9 (d, J )
2), 59.6 (d, J ) 17), 121.3 (d, J ) 3), 121.6 (d, J ) 6),
26.9, 128.0, 132.0, 132.6, 133.2 (d, J ) 28), 138.3-140.0 (m),
49.9 (d, J ) 7), 151.1 (d, J ) 9). Anal. Calcd for
H, 5.37; N, 3.73. Found: C, 47.81; H, 5.28; N, 3.61.
14-[G
2
]: white powder; 19% yield (0.079 g); 31P NMR (CH
2
-
1
Cl
(CD
48H), 5.04 (d, J ) 13.0, 12H), 7.23-7.76 (m, 93H); C NMR
(CD
2
) δ 20.8 (d, J ) 4.0), 51.7, 61.4, 61.8 (t, J ) 4.0); H NMR
3
OD) δ 1.23 (m, 72H), 3.32 (d, J ) 10.3, 27H), 3.98 (m,
13
C
1896 2472 378 381 190
H N O P S94: C, 49.99; H, 5.47; N, 11.62. Found:
C, 49.76; H, 5.32; N, 11.51.
3
OD) δ 17.3 (d, J ) 3), 34.1 (d, J ) 13), 64.7 (d, J ) 7),
Syn th esis of Ylid e-Ter m in a ted Den d r im er 11-[G
1
]. To
65.0 (d, J ) 7), 71.0 (d, J ) 165), 122.6, 123.3, 129.7, 130.2
(d, J ) 4), 134.0, 136.3, 141.2 (d, J ) 12), 151.3, 152.0 (d,
a solution of (triphenylphosphoranylidene)ethenone (0.120 g,
.397 mmol) in THF (7 mL) was added 9-[G ] (0.105 g, 0.066
-
1
0
1
J
C
)
4); IR (KBr) 3272 cm
(νOH). Anal. Calcd for
mmol) in THF (5 mL) at room temperature. The resulting
mixture was stirred for 24 h at room temperature and then
evaporated to dryness. The resulting powder was washed with
204 264 18 69 22
H N O P S10: C, 48.32; H, 5.25; N, 4.97. Found: C,
48.27; H, 5.19; N, 4.85.
14-[G
3
]: white powder; 18% yield (0.052 g); 31P NMR (CH
2
-
1
3
× 10 mL of THF/ether/pentane (1/2/2).
Cl
2
) δ 21.2 (d, J ) 3.8), 52.3, 62.2 (br s); H NMR (CD
3
OD) δ
1
1-[G
1
]: yellow powder; 78% yield (0.175 g); 31P NMR δ 18.3,
1.21 (m, 144H), 3.22 (m, 63H), 4.00 (m, 96H), 5.03 (d, J ) 12.6,
1
13
5
2.8, 62.6; H NMR δ 3.3 (s, 18H), 3.3 (d, J ) 11.5, 9H), 4.2
24H), 7.23-7.67 (m, 201H); C NMR (CD OD) δ 17.3, 34.2
3
1
3
(
(
br d, J ) 25, 6H), 7.1-7.7 (m, 135H); C NMR δ 26.8, 32.4
d, J ) 13), 32.5 (d, J ) 127), 120.9 (d, J ) 4), 126.7, 127.5,
(d, J ) 10), 64.7 (d, J ) 8), 65.0 (d, J ) 7), 71.0 (d, J ) 166),
122.6, 123.2, 130.3 (m), 134.1, 136.3, 140.5 (m), 151.0, 152.1
-
1
1
1
8
28.0 (d, J ) 12), 129.7 (d, J ) 13), 131.1, 132.4 (d, J ) 10),
33.3, 134.3, 137.5 (d, J ) 14), 149.6 (d, J ) 7), 150.4 (d, J )
(d, J ) 4); IR (KBr) 3271 cm
(νOH). Anal. Calcd for
C
432 552 42 141 46
H N O P S
22: C, 48.40; H, 5.19; N, 5.49. Found: C,
-
1
), 170.3 (d, J ) 12); IR (KBr) 1663 cm (νCdO). Anal. Calcd
48.23; H, 5.11; N, 5.37.
for C192
H
168
N
18
O
15
P
10
S
4
: C, 67.71; H, 4.97; N, 7.40. Found:
14-[G
4
]: white powder; 18% yield (0.052 g); 31P NMR (CH
2
-
1
C, 67.62; H, 4.87; N, 7.01.
Cl
2
) δ 21.2 (d, J ) 4.3), 62.2 (br s); H NMR (CD
3
OD): δ 1.21
Rea ction of Den d r im er 11-[G
solution of 0.211 mg (0.062 mmol) of dendrimer 11-[G
1
] w ith Ald eh yd es. To a
] in THF
10 mL) was added benzaldehyde (0.040 mL, 0.37 mmol) or
(m, 288H), 3.26 (m, 135H), 4.00 (m, 192H), 5.03 (d, J ) 12.7,
OD) δ 17.3, 34.0
48H), 7.25-7.67 (m, 417H); 13C NMR (CD
1
3
(
(m), 64.7 (d, J ) 7), 65.0 (d, J ) 7), 71.0 (d, J ) 166), 122.6,
130.2, 133.7-134.0 (m), 136.3, 140.0-141.5 (m), 152.1 (d, J )
crotonaldehyde (0.031 mL, 0.37 mmol). The resulting mixture
was stirred overnight at room temperature (benzaldehyde) or
for 1 week at 40 °C (crotonaldehyde). The solvent was
evaporated under vacuum to give a yellow powder that was
washed with 3 × 10 mL of THF/ether/pentane (1/2/2).
-
1
5); IR (KBr) 3270 cm
(νOH).
Anal.
Calcd for
C
888 1128 90 285 94
H N O P S46: C, 48.46; H, 5.16; N, 5.73. Found: C,
48.23; H, 5.03; N, 5.61.
14-[G
5
]: white powder; 22% yield (0.059 g); 31P NMR (CH
2
-
3
1
1
1
2-[G
1
]: pale yellow powder; 66% yield (0.097 g); P NMR
Cl
2
) δ 21.3 (d, J ) 4.5), 62.4 (br s); H NMR (CD
3
OD) δ 1.20
1
δ 52.9, 62.2; H NMR δ 3.32 (d, J ) 14.1, 9H), 3.42 (s, 18H),
(m, 576H), 3.25 (m, 279H), 4.05 (m, 384H), 5.03 (d, J ) 13.2,
1
3
13
7
1
1
1
1
6
.2-7.8 (m, 87H); C NMR δ 27.3, 27.6, 32.4 (d, J ) 12), 116.8,
17.0, 121.3 (d, J ) 6), 121.7 (d, J ) 6), 127.9, 128.1, 128.3,
28.4, 128.6, 131.9, 132.0, 137.5 (d, J ) 12), 137.6, 139.2, 142.2,
42.5, 151.0 (d, J ) 9), 151.3 (d, J ) 7), 166.3, 167.0. IR (KBr)
96H), 7.23-7.67 (m, 849H); C NMR (CD OD) δ 17.3, 34.0
3
(m), 64.7 (d, J ) 7), 65.0 (d, J ) 7), 71.0 (d, J ) 166),
122.6, 130.2, 133.8-134.1 (m), 136.3, 140.0-141.0 (m),
-
1
151.0, 152.1; IR (KBr) 3270 cm
(νOH). Anal. Calcd for
-
1
663 cm (νCdO). Anal. Calcd for C126
H
114
N
18
O
15
P
4
S
4
: C,
C H N O P S94: C, 48.48; H, 5.15; N, 5.84. Found:
1800 2280 186 573 190
C, 48.51; H, 5.09; N, 5.78.
Gen er a l P r oced u r e for th e Syn th esis of P h osp h on a te-
3.79; H, 4.84; N, 10.63. Found: C, 63.52; H, 4.71; N, 10.49.
3
1
1
3-[G
2.9, 62.2; H NMR (400 MHz, D) δ 1.80-1.90 (m, 12H,
), 3.30-3.40 (m, 27H, P NCH , C(O)NCH ), 6.05
m, (6 × 0.1)H, cis,trans-CH dCH CH dCH Me), 6.13 (dq,
1
]: pale yellow powder; 63% yield (0.08 g); P NMR δ
1
2
5
Ter m in a ted Den d r im er s 15-[G
1 5
] a n d 15-[G ]. To 0.200 g
CHdCHCH
3
1
3
3
of dendrimer 1-[G ] (n ) 1, 0.140 mmol; n ) 5, 0.0064 mmol)
n
(
d
c
b
a
were added dilauryl phosphite (n ) 1, 0.775 mL, 1.68 mmol;
n ) 5, 0.682 mL, 1.5 mmol) and then triethylamine (n ) 1, 20
µL; n ) 5, 100 µL). The resulting mixture was stirred for 3
3
3
J
HaHb ) 15.1,
J
HaCH3 ) 6.6 (6 × 0.9)H, trans,trans-CH
d
d
d
d
d
d
CH
CH
CH
CH
c
c
c
CH
CH
CH
b
b
b
dCH
dCH
dCH
a
a
a
b
Me), 6.31 (m, (6 × 0.9)H, trans,trans-CH
Me), 6.54 (m, (6 × 0.1)H, cis,trans-CH
days at room temperature (for 15-[G
temperature then for 2 days at 45 °C (for 15-[G
1
]) or for 5 days at room
]). Evapora-
3
Me), 6.80 (d, J HdHc ) 10.0, (6 × 0.1)H, cis,trans-
5
3
d
dCH
c
CH
dCH
a
Me), 7.12 (d,
J
HdHc ) 15.0, (6 × 0.9)H,
tion under vacuum gave an oil that was washed several times
with acetonitrile to give a white powder.
3
trans,trans-CH
d
dCH
c
CH
b
dCH
a
Me), 7.37 (dd,
J
HcHd ) 15.0,
3
15-[G
1
]: white powder; 16% yield (0.089 g); 31P NMR δ 21.2
7 1
J
HcHd ) 10.1, (6 × 0.9)H, trans,trans-CH
and cis,trans-CH
Me); C NMR δ 18.5, 27.4, 27.9, 32.9 (d, J ) 13),
d
dCH
c
CH
b
dCH
a
Me),
7
.20-7.80 (m, 45H, CHdN, C
CH dCH
b a
6
H
4
d
dCH
c
-
(d, J ) 3.8), 51.8, 62.2 (t, J ) 3.8); H NMR δ 0.85 (t, J ) 5.0,
36H), 1.22 (br s, 216 H), 1.40-1.55 (m, 24H), 3.30 (d, J ) 9.8,
1
3