Franc et al.
carbonate (351 mg, 1.08 mmol) in THF (5 mL). The reaction
mixture was stirred at room temperature overnight. Salts were then
removed by centrifugation, and the clear solution was concentrated
under reduced pressure. The residue was then dissolved in the
minimum amount of THF (ca.1 mL) and precipitated with a mixture
of pentane and Et2O (9:1). The resulting powder was filtered off
and then flash chromatographed to afford 4-G3 as a yellow powder
in 98% yield (270 mg). 31P-{1H} NMR (CDCl3, 121.5 MHz): δ )
7.99 (br s, PdN), 62.45 (s, P1dS, P2dS), 63.05 (s, P3dS). 1H NMR
(CDCl3, 300.13 MHz): δ ) 2.86 (br s, 96H, CaH), 3.14 (br s, 126H,
CHdN), 7.68 (s, 2H, CHdN). 13C-{1H} NMR (CDCl3, 125.8
3
3
MHz): δ ) 31.9 (d, JCP ) 12.3 Hz, CH3NP1), 32.0 (d, JCP
)
2
12.6 Hz, CH3NP1), 34.0 (s, Ca), 39.4 (s, Cb), 121.2 (br s, C’0 ),
2
2
3
121.3 (br s, C0 ), 121.43 (br s, C0 ), 128.46 (s, Ci), 128.6 (s, C0 ,
3
4
Cm), 129.9 (s, C′0 , Cp), 130.0 (s, Co), 131.18 (s, C0 ), 131.27 (s,
4
4
4
C0 ), 131.31 (s, C0 ), 135.1 (s, C′0 ), 136.3 (s, CdC), 140.7 (d,
3JCP ) 17.6 Hz, CHdNNP1), 140.7 (d, 3JCP ) 17.7 Hz, CHdNNP1),
1
1
1
148.9 (br s, C′0 ), 151.67 (br s, C0 ), 151.77 (br s, C0 ), 151.82 (br
1
s, C0 ), 170.6 (s, CdO).
Dendrimer 6-G1. A mixture of 4-hydroxybenzaldehyde (141 mg,
1.15 mmol), cesium carbonate (756.8 mg, 2.35 mmol), and
compound 7-G1 (202 mg, 0.105 mmol) in THF (10 mL) was stirred
at room temperature overnight. Salts were then removed by
centrifugation, and the clear solution was concentrated under
reduced pressure. The residue was then flash chromatographed
(THF/n-pentane, 1:1 to 1:0) to afford 6-G1 as a yellow powder in
80% yield (234 mg). 31P-{1H} NMR (CDCl3, 202.5 MHz): δ )
CH3NP1,2,3), 3.77 (br s, 96H, CbH), 6.75-7.80 (m, 882H, HAr, CHd
3
N). 13C-{1H} NMR (CDCl3, 75.46 MHz): δ ) 32.9 (br d, JCP
)
2
12.6 Hz, CH3NP1,2,3), 33.9 (s, Ca), 39.4 (s, Cb), 121.6 (br s, C0 ,
C3 ), 121.8 (br s, C1 , C2 ), 128.3 (s, C0 , C1 , C2 ), 128.5 (s, Cm,
2
2
2
3
3
3
Ci), 129.8 (s, Cp, Co), 129.9 (s, C3 ), 132.4 (br s, C0 , C1 , C2 ),
3
4
4
4
4
135.2 (s, C3 ), 136.0 (s, CdC), 138.1-139.1 (m, CHdN), 149.3
(d, JCP ) 6.9 Hz, C3 ), 151.2 (m, C0 , C1 , C2 ), 170.4 (s, CdO)
2
1
1
1
1
ppm. IR (KBr): 1700 cm-1 (νCdO).
1
8.29 (m, PdN), 60.62 (2 s, P1dS), 60.66 (s, P1dS); H NMR
Compound 5-G0. The sodium salt of 4-hydroxybenzaldehyde
(1.3 g, 9 mmol) was added to a solution of N3P3Cl6 (0.6 g, 1.73
mmol) in THF (150 mL) at 0 °C, and then the mixture was stirred
to room temperature overnight. After evaporation of the solvent,
the residue was purified by column flash chromatography (hexane/
(CDCl3, 500.3 MHz): δ ) 2.89 (t, 3JHH ) 7.8 Hz, 2H, CaH), 3.34
3
3
(d, JHP ) 10.6 Hz, 6H, CH3NP1), 3.36 (d, JHP ) 10.6 Hz, 9H,
2
CH3NP1), 3.74 (m, 2H, CbH), 6.88 (d, 3JHH ) 8.4 Hz, 2H, C′0 H),
3
2
3
6.98 (d, JHH ) 8.6 Hz, 4H, C0 H), 7.05 (d, JHH ) 8.4 Hz, 2H,
3
3
2
C′0 H), 7.09 (d, JHH ) 8.6 Hz, 6H, C0 H), 7.34-7.42 (m, 30H,
2
3
ethyl acetate 5:1) to give 5-G0 as a colorless oil in 85% yield (1.13
C1 H, CoH, CmH, CpH), 7.55-7.63 (m, 10H, C0 H), 7.65 (s, 3H,
2
3
g). 31P{1H} NMR (CDCl3, 121.50 MHz): δ ) 3.53 (2 d, JPP
)
CHdN), 7.68 (s, 2H, CHdN), 7.81-7.86 (m, 20H, C1 H), 9.91
2
2
2
88.1 Hz, JPP ) 85.0 Hz, P0), 19.09 (dd, JPP ) 88.1 Hz, JPP
)
(s, 2H, CHO), 9.92 (s, 2H, CHO), 9.93 (s, 4H, CHO), 9.93 (s, 2H,
1
85.0 Hz, P′0). H NMR (CD3OCD3-d6, 300.13 MHz): δ ) 7.24
CHO). 13C-{1H} NMR (CDCl3, 125.8 MHz): δ ) 32.9 (br d, 3JCP
2
3
2
(m, 10H, C0 H), 7.79 (m, 10H, C0 H), 9.95 (3 s; 5H, CHO). 13C-
) 12.6 Hz, CH3NP1), 33.9 (s, Ca), 39.3 (s, Cb), 121.1 (br s, C’0 ),
2
2
2
2
{1H} NMR (CDCl3, 75.48 MHz): δ ) 121.6 (m, C0 ), 131.5 (s,
121.3 (br s, C0 ), 121.5 (br s, C0 ), 122.0 (br s, C1 ), 128.29 (s,
3
4
4
1
3
3
C0 ), 133.9 (s, C0 ), 134.0 (s, C0 ), 154.3 (d, 2JCP ) 17.1 Hz, C0 ),
C0 ), 128.32 (s, C0 ), 128.4 (s, Ci), 128.6 (s, Cm), 129.81 (s, Co),
3
3
4
190.4 (s, CHO), 190.5 (s, CHO) ppm.
129.85 (s, Cp), 130.0 (s, C′0 ), 131.5 (br s, C1 ), 131.7 (s, C0 ),
4
4
4
131.8 (s, C0 ), 133.7 (s, C1 ), 135.2 (s, C′0 ), 136.1 (s, CdC), 139.5
(s, CHdNNP1), 149.0 (s, C′0 ), 151.4 (br s, C0 ), 151.6 (br s, C0 ),
154.99 (s, C1 ), 155.05 (s, C1 ), 155.09 (s, C1 ), 170.5 (s, CdO),
190.72 (s, CHO), 190.74 (s, CHO) ppm.
Dendrimer 6-G0. Cesium carbonate (656 mg, 1 mmol) and
compound 5-G0 (780 mg, 1 mmol) were added to a solution of 1
(370 mg, 1 mmol) in acetone (5 mL). The reaction mixture was
stirred overnight at room temperature and then centrifuged. The
supernatant was then concentrated under reduced pressure. The
resulting yellow oil was flash chromatographed to afford 6-G0 as
a yellow powder in 85% yield (947 mg). 31P-{1H} NMR (CDCl3,
121.50 MHz): δ ) 8.04 (m, PdN). 1H NMR (CDCl3, 500.3
MHz): δ ) 3.03 (t, 3JHH ) 7.3 Hz, 2H, CaH), 3.88 (t, 3JHH ) 7.3
1
1
1
1
1
1
Dendrimer 7-G2. A freshly prepared solution (0.16 mmol in
chloroform) of N-methyldichlorothiophosphorhydrazide (6.4 mL)
was added at 0 °C to compound 6-G1 (260 mg, 0.094 mmol). The
reaction mixture was stirred at room temperature until completion
(ca. 40 min) and then precipitated with pentane. The powder was
filtered off, dissolved in the minimum amount of THF (ca. 1 mL),
and precipitated with pentane. These washings were repeated thrice
to afford 7-G2 as a yellow powder in 76% yield (313 mg). 31P-
{1H} NMR (CDCl3, 121.49 MHz): δ ) 8.35 (m, PdN), 61.95 (s,
P1dS), 61.99 (s, P1dS), 62.80 (s, P2dS), 62.83 (s, P2dS), 62.85
2
Hz, 2H, CbH), 7.06 (d, 3JHH ) 8.5 Hz, 2H, C′0 H), 7.24-7.29 (m,
12H, C0 H, C′0 H), 7.35-7.46 (m, 10H, CoH, CmH, CpH), 7.81-
2
3
3
7.89 (m, 10H, C0 H), 9.98 (s, 1H, CHO), 9.99 (s, 2H, CHO), 10.00
(s, 2H, CHO). 13C-{1H} NMR (CDCl3, 125.8 MHz): δ ) 33.4 (s,
Ca), 39.2 (s, Cb), 120.8 (m, C′0 ), 121.3 (m, C0 ), 128.3 (s, Co),
2
2
3
1
3
129.1 (s, Ci), 129.6 (s, Cp), 129.8 (s, Cm), 130.2 (s, C′0 ), 131.21
(s, P2dS); H NMR (CDCl3, 300.13 MHz): δ ) 2.89 (t, JHH )
3
3
3
3
4
(s, C0 ), 131.24 (s, C0 ), 131.26 (s, C0 ), 134.06 (s, C0 ), 134.15 (s,
C0 ), 134.17 (s, C0 ), 136.3 (s, C′0 ), 136.4 (s, CdC), 148.8 (m,
C′0 ), 154.5 (m, C0 ), 154.7 (m, C0 ), 170.2 (s, CdO), 190.49 (s,
CHO), 190.55 (s, CHO) ppm. IR(KBr): 1702 cm-1 (νCdO). MS
(FAB) m/z ) 1109 [MH]+.
8.4 Hz, 2H, CaH), 3.32 (m, 15H, CH3NP1), 3.43 (d, JHP ) 13.8
4
4
4
3
Hz, 12H, CH3NP2), 3.44 (d, JHP ) 13.8 Hz, 18H, CH3NP2), 3.76
1
1
1
3
3
2
(t, JHH ) 8.4 Hz, 2H, CbH), 6.92 (d, JHH ) 8.1 Hz, 2H, C′0 H),
2
3
2
7.00 (d, 3JHH ) 8.4 Hz, 4H, C0 H), 6.98-7.08 (m, 8H, C′0 H, C0 H),
2
7.22-7.28 (m, 20H, C1 H), 7.30-7.43 (m, 10H, CoH, CmH, CpH),
3
3
7.57-7.71 (m, 45H, C0 H, C1 H, CHdN). 13C-{1H} NMR (CDCl3,
Dendrimer 7-G1. A freshly prepared solution (0.24 mol‚L-1 in
chloroform) of N-methyldichlorothiophosphorhydrazide (7 mL, 1.68
mmol) was added at 0 °C to a solution of 6-G0 (310 mg, 0.279
mmol) in chloroform (1 mL). The solution was stirred for 3 h and
then concentrated under reduced pressure (ca. 1 mL). A 20 mL
portion of pentane was added to the residue, and the resulting
precipitate was filtered off and dried under reduced pressure. The
powder was finally dissolved in the minimum amount of CH2Cl2
and precipitated with pentane to afford 7-G1 as a yellow powder
in 91% yield (486 mg). 31P-{1H} NMR (CDCl3, 81.0 MHz): δ )
8.52 (m, PdN), 62.60 (s, P1dS), 62.67 (s, P1dS), 62.71 (s, P1d
75.46 MHz): δ ) 31.9 (d, 3JCP ) 13.1 Hz, CH3NP1), 33.1 (d, 3JCP
2
) 12.5 Hz, CH3NP2), 33.9 (s, Ca), 39.4 (s, Cb), 121.1 (br s, C′0 ),
2
2
3
121.4 (br s, C0 ), 121.9 (br s, C1 ), 128.3 (s, C0 ), 128.4 (s, Ci),
3
3
128.6 (s, Cm), 128.8 (br s, C1 ), 129.8 (s, Co, Cp), 130.0 (s, C′0 ),
4
4
4
4
131.6 (s, C1 ), 131.9 (s, C0 ), 132.0 (s, C0 ), 135.2 (s, C′0 ), 136.1
(s, CdC), 139.0 (d, 3JCP ) 13.6 Hz, CHdNNP1), 140.6 (d, 3JCP
)
1
1
18.8 Hz, CHdNNP2), 149.0 (s, C′0 ), 151.4 (br s, C0 ), 151.8 (m,
1
C1 ), 170.5 (s, CdO) ppm.
Dendrimer 6-G2. A mixture of 4-hydroxybenzaldehyde (155 mg,
1.27 mmol), cesium carbonate (825 mg, 2.53 mmol), and compound
7-G2 (250 mg, 0.057 mmol) in THF (10 mL) was stirred at room
temperature overnight. Salts were then removed by centrifugation,
and the clear solution was concentrated under reduced pressure.
The residue was then flash chromatographed (ether/THF 1:0 to 1:1)
to afford 6-G2 as a yellow powder in 72% yield (248 mg). 31P-
{1H} NMR (CDCl3, 121.49 MHz): δ ) 8.35 (m, PdN), 60.27 (s,
P2dS), 60.30 (s, P2dS), 62.23 (s, P1dS), 62.29 (s, P1dS). 1H NMR
1
3
S); H NMR (CDCl3, 500.3 MHz): δ ) 2.95 (t, JHH ) 7.8 Hz,
2H, CaH), 3.45 (d, 3JHP ) 13.9 Hz, 6H, CH3NP1), 3.48 (d, 3JHP
13.8 Hz, 9H, CH3NP1), 3.80 (t, 3JHH ) 7.8 Hz, 2H, CbH), 6.92 (d,
)
2
3
2
3JHH ) 8.3 Hz, 2H, C′0 H), 6.98 (d, JHH ) 8.7 Hz, 4H, C0 H),
3
2
3
7.07 (d, JHH ) 8.7 Hz, 6H, C0 H), 7.08 (d, JHH ) 8.3 Hz, 2H,
3
C′0 H), 7.35-7.48 (m, 10H, CoH, CmH, CpH), 7.60 (d, 3JHH ) 8.7
3
3
3
Hz, 4H, C0 H), 7.62 (d, JHH ) 8.7 Hz, 6H, C0 H), 7.65 (s, 3H,
8714 J. Org. Chem., Vol. 72, No. 23, 2007