washed with 5 ꢂ 20 ml of water. The organic phase was dried
over sodium sulfate, then filtered and evaporated under va-
cuum. The product was purified by chromatography on a
silica-gel column with a pentane–diethyl ether mixture (8 : 2)
to provide 19 (2.767 g, 75%) as a colorless solid. 1H NMR
(CDCl3, 200.16 MHz) dppm: d 7.24 (d, 6H, Ar), 6.93 (d, 2H,
Ar), 6.98 (d, 6H, Ar), 5.57 (m, 9H, CHQCH2), 5.03 (m, 24H,
CHQCH2, and CH2O), 2.46 (s, 9H, CH3), 2.44 (d, 18H,
CH2CHQCH2). 13C NMR (CDCl3, 62.91 MHz) dppmu
157.07 (Cq, ArO), 139.35 (Cq, arom), 138.04 (Cq, arom), 134.72
(CHQCH2), 131.92 (Cq, arom), 127.73 (CHarom), 117.57
(CHQCH2), 114.08 (CHarom), 64.88 (CH2O), 42.71 (Cq–CH2),
42.03 (CH2), 16.01 (CH3). MALDI TOF mass spectrum, m/z:
863.43 [M + Na]+ (calcd 864.21). Elemental analysis calcd for
C60H72O3: C, 85.67; H, 8.63. Found: C, 85.31; H, 8.47%.
(CDCl3, 62.91 MHz): d = 157.27 (Cq, ArO), 139.25 (Cq, arom),
138.68 (Cq, arom), 134.91 (Cq, arom), 127.23 (CHarom), 114.48
(CHarom), 62.59 (CH2O), 59.45 (CH2–N), 31.48
(CH2–CH2–N), 26.93 (CH2–Cq), 25.95 (CH2), 22.53, (CH2),
22.21 (CH2), 13.93 (CH3). Elemental analysis calcd for
C164H305O3I9N9: C, 54.79; H, 8.55. Found: C, 55.04; H,
8.74%.
Nona-ammonium nona-tetrafluoroborate dendrimer 24. Den-
drimer 24 was obtained from the salt 23, in 90% yield using
1
the procedure described for 6. H NMR (200 MHz, CDCl3)
dppm: 7.26 (sbroad, 6H, Harom), 6.95 (sbroad, 6H, Harom), 5.05
(sbroad, 6H, CH2O), 3.34 (mbroad, N–CH2), 1.75–1.53 (mbroad
,
N–CH2–CH2), 1.27 (mbroad, CH2), 0.85 (mbroad, CH3). 13C
NMR (CDCl3, 62.91 MHz) dppm: 157.27 (Cq, ArO), 139.25
(Cq, arom), 138.68 (Cq, arom), 134.91 (Cq, arom), 127.23 (CHarom),
114.48 (CHarom), 62.59 (CH2O), 58.81 (CH2–N), 31.08
(CH2–CH2–N). Elemental analysis calcd for C164H305O3I9N9
B9F36: C, 60.94; H, 9.51. Found: C, 60.32, H, 9.15%.
Nona-ol dendrimer 20. Dendrimer 20 was obtained as a
colorless solid in 95% yield from the nona-allyl 19, using the
procedure described in ref. 14. 1H NMR (CD3OD, 200.16
MHz) dppm: 7.12 (d, 6H, Ar), 6.80 (d, 2H, Ar), 4.90 (s, 6H,
CH2O), 3.28 (t, 18H, CH2O), 1.55 (m, 18H, CH2), 1.12 (m,
18H, CH2). 13C NMR (CD3OD, 62.91 MHz) dppm: 156.79 (Cq,
ArO), 139.31 (Cq, arom), 138.68 (Cq, arom), 131.76 (Cq, arom),
127.23 (CHarom), 113.76 (CHarom), 62.14 (CH2O), 41.41
(Cq–CH2), 33.28 (CH2), 26.40 (CH2), 14.57 (CH3). MALDI
TOF mass spectrum, m/z: 1025.88 [M + Na]+ (calcd
1026.35). Elemental analysis calcd for C60H90O12: C, 71.81;
H, 9.04. Found: C, 71.09; H, 9.22%.
Tris(POM) dendrimer 25. This dendrimer was obtained as a
colorless solid in 75% yield from the nona-ammonium salt 24
using the procedure described above for 7. 1H NMR (CDCl3,
200.16 MHz) dppm: 7.2 (d, 6H, Ar), 7.01 (d, 6H, Ar), 5.13
(s, 6H, CH2O), 3.3 (mbroad, CH2–N), 1.85–1.66 (mbroad
,
N–CH2–CH2), 1.36 (mbroad, CH2), 0.91 (m, CH3). 13C NMR
(CDCl3, 62.91 MHz) dppm: 157.27 (Cq, ArO), 139.25 (Cq, arom),
138.68 (Cq, arom), 134.91 (Cq, arom), 127.23 (CHarom), 114.48
(CHarom),
62.59
(CH2O),
59.45
(CH2–N),
31.48
Nona-mesylate dendrimer 21. Dendrimer 21 was obtained as
a yellow oil in 98% yield from the nona-ol 20, using the
procedure described in ref. 14. 1H NMR (CDCl3, 200.16
MHz) dppm: 7.20 (d, 6H, Ar), 6.96 (d, 2H, Ar), 5.08
(s, 6H, CH2O), 4.15 (t, 18H, CH2O), 2.97 (s, 27H, CH3SO2),
1.75 (mbroad, 18H, CH2), 1.53 (mbroad, 18H, CH2). 13C NMR
(CDCl3, 62.91 MHz) dppm: 157.27 (Cq, ArO), 139.25 (Cq, arom),
138.68 (Cq, arom), 134.91 (Cq, arom), 127.23 (CHarom), 114.48
(CHarom), 70.47 (CH2OSO2), 62.59 (CH2O), 41.67 (Cq–CH2),
37.37 (SO2CH3), 23.59 (CH2), 15.98 (CH3). Elemental analysis
calcd for C69H108O30S9: C, 48.57; H, 6.38. Found: C, 48.78; H,
6.40%.
(CH2–CH2–N), 31.02 (CH3), 26.93 (CH2–Cq), 25.95 (CH2),
22.53, (CH2), 22.21 (CH2), 13.93 (CH3). 31P NMR (CDCl3, 81
MHz) dppm: 3.12 (PO4). FTIR (KBr plates) ncmꢀ1: 1076 and
1058 (P–O), 963 (WQO), 830 (O–O), 580 and 521 W(O2)s,as
Elemental analysis calcd for C219H436O75N9 P3W12: C, 39.29;
.
H, 6.56; P, 1.39. Found: C, 39.90; H, 6.58; P, 1.35%.
Hexa-allyl dendrimer 26. This dendrimer was obtained as a
white solid in 90% yield using the procedure described above
1
for the nona-allyl 19. H NMR (CDCl3, 200.16 MHz) dppm
7.47 (s, 4H, Ar), 7.23 (d, 4H, Ar), 6.94 (d, 4H, Ar), 5.57 (m,
:
6H, CHQCH2), 5.03 (m, 16H, CHQCH2, and CH2O), 2.43
(d, 9H, CH2CHQCH2). 13C NMR (CDCl3, 62.91 MHz) dppm
:
Nona-iodo dendrimer 22. This dendrimer was obtained as a
yellow oil in 95% yield from the nona-mesylate 21 using the
procedure described in ref. 14. 1H NMR (CDCl3, 200.16
MHz) dppm: 7.28 (d, 6H, Ar), 7.02 (d, 2H, Ar), 5.13 (s, 6H,
156.69 (Cq, ArO), 138.10 (Cq, arom), 136.95 (Cq, arom), 134.68
(CHQCH2), 127.81 (Cq, arom), 127.75 (CHarom), 117.57
(CHQCH2), 114.08 (CHarom), 69.72 (CH2O), 42.74 (Cq–CH2),
41.99 (CH2). MALDI TOF mass spectrum, m/z: 581.13 [M +
Na]+ (calcd 581.79). Elemental analysis calcd for C40H46O2:
C, 85.98; H, 8.30. Found: C, 85.86; H, 8.34%.
CH2O), 3.18 (t, 18H, CH2I), 2.51 (s, 9H, CH3), 1.78 (mbroad
,
18H, CH2), 1.65 (mbroad, 18H, CH2). 13C NMR (CDCl3,
62.91 MHz) dppm: 157.16 (Cq, ArO), 139.30 (Cq, arom),
137.94 (Cq, arom), 131.75 (Cq, arom), 127.15 (CHarom), 114.35
(CHarom), 64.86 (CH2O), 41.71 (Cq–CH2), 38.52 (CH2), 27.55
(CH2), 16.03 (CH3), 7.89 (CH2I). Elemental analysis calcd for
C60H81O3I9: C, 36.17; H, 4.10. Found: C, 36.75; H, 4.56%.
Hexa-ol dendrimer 27. The hexa-ol 27 was obtained as a
colorless solid in 90% yield from 26 using the procedure
1
described in ref. 14. H NMR (CD3OD, 200.16 MHz) dppm
:
7.43 (s, 4H, Ar), 7.20 (d, 4H, Ar), 7.95 (d, 4H, Ar), 5.03 (s, 4H,
CH2O), 3.46 (t, 12H, CH2O), 1.65 (m, 12H, CH2), 1.30 (m,
12H, CH2). 13C NMR (CD3OD, 62.91 MHz) dppm: 156.50 (Cq,
ArO), 139.19 (Cq, arom), 137.03 (Cq, arom), 127.13 (CHarom),
113.90 (CHarom), 69.17 (CH2O), 62.10 (CH2O), 41.34
(Cq–CH2), 33.25 (CH2), 26.37 (CH2). MALDI TOF mass
spectrum, m/z: 689.65 [M + Na]+ (calcd 689.88). Elemental
Nona-ammonium nona-iodide dendritic salt 23. This dendritic
salt was obtained from the nona-iodo derivative 22, in 93%
1
yield using the procedure described for 5. H NMR (CDCl3,
200.16 MHz) dppm: 7.28 (d, 6H, Ar), 7.01 (d, 6H, Ar), 5.13
(s, 6H, CH2O), 3.3 (mbroad, CH2–N), 1.85-1.66 (mbroad
,
N–CH2–CH2), 1.36 (mbroad, CH2), 0.91 (m, CH3). 13C NMR
ꢁc
This journal is the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2007
1272 | New J. Chem., 2007, 31, 1264–1274