Synthesis and characterization of phosphorus dendrimers containing long, conjugated branches

Article abstract of DOI:10.1002/ejoc.200400679

The synthesis of a new family of phosphorus dendrimers is described up to the fifth generation (96 end-groups). The reaction is based on the nucleophilic substitution of P(S)Cl₂ end-groups by 4-hydroxy-3- methoxycinnarnaldehyde, and by the condensation of CHO end-groups with a dichlorophosphorhydrazide. The structure of the first generation has been determined by X-ray diffraction. This structure shows that the OC ₆H₃CH=CHCH=NNMeP(S) linkage is close to planarity, which indicates an extended conjugation of this linkage that leads to a semi-rigid skeleton for these dendrimers. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejoc.200400679

FULL PAPER
Synthesis and Characterization of Phosphorus Dendrimers Containing Long,
Conjugated Branches
Germinal Magro,[a] Patrice Marchand,[a] Rosa-María Sebastián,[a]
Carine Guyard-Duhayon,[a] Anne-Marie Caminade,*[a] and Jean-Pierre Majoral*[a]
Dedicated to Prof. Dr. Michael Veith on the occasion of his 60th birthday
Keywords: Aldehydes / Dendrimers / Hydrazones / Main-group elements / Phosphorus
The synthesis of a new family of phosphorus dendrimers is
described up to the fifth generation (96 end-groups). The re-
action is based on the nucleophilic substitution of P(S)Cl2
end-groups by 4-hydroxy-3-methoxycinnamaldehyde, and
by the condensation of CHO end-groups with a dichloro-
phosphorhydrazide. The structure of the first generation has
been determined by X-ray diffraction. This structure shows
that the OC6H3CH=CHCH=NNMeP(S) linkage is close to
planarity, which indicates an extended conjugation of this
linkage that leads to a semi-rigid skeleton for these dendri-
mers.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
structure. The rigid part is due to the conjugated
OC6H4CH=NNMeP(S) moieties, in which all atoms lie ap-
proximately in the same plane.[12] These phosphorus dendri-
mers possess many original properties in various fields such
as the modification[13] or creation[14] of materials, cataly-
sis,[15] or various biological uses.[16] In most cases, the hy-
drophobicity and the semi-rigidity of the interior of these
dendrimers is believed to play a key role in determining
their properties. If this semi-rigidity could be found also for
longer branches, some properties of these dendrimers could
be modified, particularly those connected to the size of the
internal cavities or those connected to the density of end-
groups. In order to be able to detect the modifications in-
duced by the lengthening of the branches without changing
other parameters, we decided to build dendrimers from 4-
hydroxy-3-methoxycinnamaldehyde instead of the 4-hy-
droxybenzaldehyde used in our classical method of synthe-
sis.[11] We report here the synthesis and characterization of
this new series of semi-rigid dendrimers up to generation 5,
as well as the crystal structure of the first generation ob-
tained by X-ray diffraction.
Introduction
Dendrimers are a very special type of hyperbranched and
monodisperse polymers that are built step by step by the
repetition of a sequence of reactions.[1–3] They constitute
one of the most important new fields of research in chemis-
try, as shown by the large number of publications, patents
or reports listed in Chemical Abstracts (more than 7000),
97% of them having been published within the last ten
years. In more recent years the emphasis has been mainly
on the properties and applications of dendrimers, although
a large part of the work is still devoted to synthesis. In most
cases, the synthetic aspects mainly concern modification of
the end-groups, whereas changes of the monomeric units
constituting the skeleton of dendrimers remain rare. How-
ever, the nature of the interior plays an important role in
the properties of dendrimers, particularly in terms of flexi-
bility or rigidity, which dictates the possibility or not for
the end-groups to be backfolded.[4] PAMAM,[5] PPI,[6] or
polysiloxane[7] dendrimers and arborols[8] have flexible
branches, constituted at least in part of alkyl linkages,
whereas poly(aryl ether) dendrimers[9] are less flexible, and
polyphenylene dendrimers[10] possess a highly rigid skel-
eton. The phosphorus dendrimers we synthesize[11] have
some of the longest branches, constituted of P(S)
OC6H4CH=NNMeP(S) linkages, which afford a semi-rigid
Results and Discussion
The first step of the synthesis is the nucleophilic substitu-
tion of the three chlorines of P(S)Cl3 (1-G0) by 4-hydroxy-
3-methoxycinnamaldehyde (2) under basic conditions. Two
methods were used, but the reaction is very slow in both
cases. The first method consists of reacting the cinnamal-
dehyde 2 and P(S)Cl3 in THF, in the presence of Cs2CO3,
[a] Laboratoire de Chimie de Coordination CNRS,
205 route de Narbonne, 31077 Toulouse Cedex 4, France
Fax: +33-5-61-55-30-03
E-mail: caminade@lcc-toulouse.fr,
majoral@lcc-toulouse.fr
1340
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400679
Eur. J. Org. Chem. 2005, 1340–1347

Phosphorus Dendrimers Containing Long, Conjugated Branches
FULL PAPER
for three days at room temperature. Under these conditions,
dendrimer 1-G0Ј was isolated in 52% yield after workup.
The second method necessitates the preliminary synthesis
of the sodium salt of 4-hydroxy-3-methoxycinnamaldehyde
(2-Na), which is obtained by reaction of NaH with 2 in
THF. A heterogeneous solution of this sodium salt in THF
reacts with P(S)Cl3 at 40 °C and this reaction needs five
days to go to completion, as shown by 31P NMR monitor-
ing of the crude solution; compound 1-G0Ј was isolated in
63% yield after workup (Scheme 1). This reaction is very
slow, especially when compared to that involving the so-
dium salt of 4-hydroxybenzaldehyde, which reacts in a few
hours at room temperature with P(S)Cl3.[11] Thus, the meth-
oxy group in the ortho position relative to the site of the
reaction seems to have a major influence on the reaction
rate.
Scheme 1.
The condensation reaction between the aldehyde groups
of 1-G0Ј and the phosphorhydrazide 3 is more rapid and
occurs in 24 h at room temperature. The first generation of angles in Table 2. Despite the long time needed for the nu-
the dendrimer, 1-G1, was isolated in good yield after work- cleophilic substitution, it appears that there is no particular
up (90%). The condensation reaction induces the total dis- steric hindrance at the level of the core because the three
appearance of the signals corresponding to the aldehydes in methoxy groups move away from the central phosphorus
1
the H and 13C NMR spectra, as well as in the IR spectra. (P1). Thus, the slowness of the nucleophilic substitution ob-
Furthermore, this reaction induces the appearance of a new served for the synthesis of 1-G0Ј is more likely due to the
signal in the 31P NMR spectrum at δ = 61.3 ppm, which electronic influence of the methoxy group than to its steric
corresponds to the P(S)Cl2 end-groups, besides the signal influence. The arrangement of atoms close to the core is
at δ = 54.6 ppm corresponding to the core. In order to as- relatively symmetric, but all three branches of 1-G1 are dif-
certain the structure of dendrimer 1-G1, and, especially, to ferent in the crystal, contrary to the structure of the related
know whether the expected semi-rigidity of the lengthened compound (S)P[OC6H4CH=NNMeP(S)Cl2]3 (4-G1), which
branches is observed or not, single crystals suitable for X- has also been determined by X-ray diffraction and which
ray diffraction were grown from acetonitrile solution.
has the symmetrical structure of a three-blade propeller.[12]
The CAMERON drawing of compound 1-G1 is shown However, all three OC6H3CH=CHCH=NNMeP branches
in Figure 1; bond lengths are given in Table 1, and bond are relatively planar, thus illustrating the expected rigidity
Figure 1. CAMERON drawing of 1-G1.
Eur. J. Org. Chem. 2005, 1340–1347
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1341

A.-M. Caminade, J.-P. Majoral et al.
Table 2. Bond angles (°) for 1-G1.
FULL PAPER
Table 1. Bond lengths (Å) for 1-G1.
S(1)–P(1)–O(1)
117.2(3)
118.4(2)
100.3(3)
117.3(3)
99.8(3)
C(23)–C(24)–C(25)
C(23)–C(24)–C(28)
C(25)–C(24)–C(28)
C(24)–C(25)–C(26)
C(21)–C(26)–C(25)
C(24)–C(28)–C(29)
C(28)–C(29)–C(30)
C(29)–C(30)–N(21)
C(30)–N(21)–N(22)
P(22)–N(22)–C(31)
P(22)–N(22)–N(21)
C(31)–N(22)–N(21)
P(1)–O(21)–C(21)
C(22)–O(22)–C(27)
S(42)–P(42)–Cl(41)
S(42)–P(42)–Cl(42)
Cl(41)–P(42)–Cl(42)
S(42)–P(42)–N(42)
Cl(41)–P(42)–N(42)
Cl(42)–P(42)–N(42)
C(42)–C(41)–C(46)
C(42)–C(41)–O(41)
C(46)–C(41)–O(41)
C(41)–C(42)–C(43)
C(41)–C(42)–O(42)
C(43)–C(42)–O(42)
C(42)–C(43)–C(44)
C(43)–C(44)–C(45)
C(43)–C(44)–C(48)
C(45)–C(44)–C(48)
C(44)–C(45)–C(46)
C(41)–C(46)–C(45)
C(44)–C(48)–C(49)
C(48)–C(49)–C(50)
C(49)–C(50)–N(41)
C(50)–N(41)–N(42)
P(42)–N(42)–C(51)
P(42)–N(42)–N(41)
C(51)–N(42)–N(41)
P(1)–O(41)–C(41)
C(42)–O(42)–C(47)
120.0(8)
120.6(8)
119.4(8)
119.4(9)
119.2(8)
125.7(10)
122.3(10)
116.5(9)
117.5(9)
125.1(7)
112.9(7)
121.7(8)
126.6(5)
117.8(7)
114.43(17)
115.51(18)
100.05(17)
114.9(3)
105.9(3)
104.4(3)
121.2(8)
116.8(7)
121.9(8)
119.6(7)
115.0(7)
125.3(8)
120.4(8)
118.9(7)
119.7(8)
121.4(7)
120.6(8)
119.3(8)
126.2(9)
123.6(9)
117.1(8)
118.0(8)
124.3(6)
113.3(6)
122.3(7)
123.9(5)
117.4(6)
P(1)–S(1)
1.888(4)
1.573(6)
1.572(6)
1.579(6)
1.887(4)
2.020(5)
1.989(4)
1.644(8)
1.375(11)
1.381(11)
1.407(10)
1.387(12)
1.378(10)
1.387(11)
1.397(12)
1.463(13)
1.364(12)
1.410(10)
1.338(12)
1.431(12)
1.278(11)
1.460(11)
1.408(10)
1.885(4)
2.012(4)
1.990(4)
1.644(8)
1.386(11)
1.357(11)
1.409(9)
1.382(11)
C(22)–O(22)
C(23)–C(24)
C(24)–C(25)
C(24)–C(28)
C(25)–C(26)
C(27)–O(22)
C(28)–C(29)
C(29)–C(30)
C(30)–N(21)
C(31)–N(22)
N(21)–N(22)
P(42)–S(42)
P(42)–Cl(41)
P(42)–Cl(42)
P(42)–N(42)
C(41)–C(42)
C(41)–C(46)
C(41)–O(41)
C(42)–C(43)
C(42)–O(42)
C(43)–C(44)
C(44)–C(45)
C(44)–C(48)
C(45)–C(46)
C(47)–O(42)
C(48)–C(49)
C(49)–C(50)
C(50)–N(41)
C(51)–N(42)
N(41)–N(42)
1.360(10)
1.395(12)
1.401(11)
1.480(12)
1.396(12)
1.427(12)
1.338(12)
1.460(13)
1.272(11)
1.449(13)
1.420(11)
1.904(3)
S(1)–P(1)–O(21)
O(1)–P(1)–O(21)
S(1)–P(1)–O(41)
O(1)–P(1)–O(41)
O(21)–P(1)–O(41)
S(2)–P(2)–Cl(1)
S(2)–P(2)–Cl(2)
Cl(1)–P(2)–Cl(2)
S(2)–P(2)–N(2)
C(1)–C(2)–C(3)
C(1)–C(2)–O(2)
C(3)–C(2)–O(2)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(3)–C(4)–C(8)
C(5)–C(4)–C(8)
C(4)–C(5)–C(6)
C(1)–C(6)–C(5)
C(4)–C(8)–C(9)
C(8)–C(9)–C(10)
C(9)–C(10)–N(1)
C(10)–N(1)–N(2)
P(2)–N(2)–C(11)
P(2)–N(2)–N(1)
C(11)–N(2)–N(1)
P(1)–O(1)–C(1)
C(2)–O(2)–C(7)
S(22)–P(22)–Cl(21)
S(22)–P(22)–Cl(22)
Cl(21)–P(22)–Cl(22)
S(22)–P(22)–N(22)
Cl(21)–P(22)–N(22)
Cl(22)–P(22)–N(22)
C(22)–C(21)–C(26)
C(22)–C(21)–O(21)
C(26)–C(21)–O(21)
C(21)–C(22)–C(23)
C(21)–C(22)–O(22)
C(23)–C(22)–O(22)
C(22)–C(23)–C(24)
P(1)–O(1)
P(1)–O(21)
P(1)–O(41)
P(2)–S(2)
100.4(3)
113.5(2)
115.1(2)
101.0(2)
115.8(3)
118.6(8)
116.0(8)
125.4(8)
121.3(8)
118.4(9)
119.6(8)
122.0(8)
120.6(8)
120.0(8)
128.2(8)
122.7(8)
119.1(8)
118.8(8)
122.7(7)
113.5(6)
121.0(7)
127.3(5)
117.7(7)
113.7(2)
115.4(2)
99.85(19)
115.7(3)
104.2(3)
106.1(3)
122.3(8)
114.7(8)
122.2(7)
119.2(8)
115.5(7)
125.3(8)
119.6(8)
P(2)–Cl(1)
P(2)–Cl(2)
P(2)–N(2)
C(1)–C(2)
C(1)–C(6)
C(1)–O(1)
C(2)–C(3)
C(2)–O(2)
C(3)–C(4)
C(4)–C(5)
C(4)–C(8)
C(5)–C(6)
C(7)–O(2)
C(8)–C(9)
C(9)–C(10)
C(10)–N(1)
C(11)–N(2)
N(1)–N(2)
P(22)–S(22)
P(22)–Cl(21)
P(22)–Cl(22)
P(22)–N(22)
C(21)–C(22)
C(21)–C(26)
C(21)–O(21)
C(22)–C(23)
2.001(4)
2.012(4)
1.643(7)
1.380(11)
1.383(11)
1.392(9)
1.381(11)
1.377(9)
1.397(11)
1.401(12)
1.454(11)
1.380(11)
1.427(10)
1.331(11)
1.441(12)
1.286(10)
1.455(11)
1.411(9)
of this linkage. The branch linked to P2 is the most planar:
the maximum deviations to the mean plane defined by the
aromatic ring are –0.268 Å for P2 and 0.169 Å for O1; the
branch linked to P22 is the least planar: the maximum devi-
ations to the mean plane defined by the aromatic ring are phorus that undergo the reaction, from δ = 61.3 ppm for 1-
1.976 Å for P22 and 1.343 Å for N22. All the CH=CH– G1 to δ = 62.0 ppm for 1-G1Ј in the 31P NMR spectra. The
CH=N linkages retain the all-trans configuration, thereby 1H NMR spectrum of 1-GЈ1 shows that the CH=CH link-
ensuring a maximum elongation of the branches. To the ages included in CH=CH–CH=O and in CH=CH–CH=N
best of our knowledge, these arms are the longest ever re- linkages have retained their (E)-configuration as expected,
3
ported for dendrimers characterized by X-ray diffraction as shown by the value of the JH,H coupling constant
(P1···P2 = 12.20 Å, P1··P22 = 12.49 Å, P1···P42 = 12.02 Å (15.9 Hz). The condensation reaction with the phosphorhy-
for dendrimer 1-G1; cf 9 Å for 4-G1). Furthermore, the dis- drazide 3 and the nucleophilic substitution were each re-
tance between two arms in the same molecule is large peated four times from 1-G1Ј to afford finally the fifth gen-
(P2···P22 = 17.02 Å, P22···P42 = 23.86 Å, P42···P2 = eration dendrimer 1-G5Ј (96 aldehyde end-groups;
20.82 Å for dendrimer 1-G1; cf 17 Å for 4-G1). In the pack- Scheme 2).
ing, two molecules appear to interact through two aromatic
In all cases the nucleophilic substitution is slow, but we
groups of each dendrimers (π–π interactions; Figure 2). In do not observe a lengthening of the reaction time with in-
addition, short distances are found between the central sul- creasing generations. This suggests that there is no increase
fur atom (S1) of one molecule and a chlorine (Cl41) of an- in the steric hindrance, and the slowness of the reaction is
other molecule, as well as between two chlorines of two due to electronic influences and not to steric constraints.
molecules (Cl42 and Cl21) (Figure 3).
Obviously, all the intermediate compounds shown in
The very large distance between each end-group found Scheme 2 were isolated and characterized by multinuclear
in 1-G1 indicates that there should be no particular problem NMR and IR spectroscopy, and elemental analysis. 31P
to continue the growth of the dendrimer. Starting from 1- NMR spectroscopy appears, as usual, to be a very sensitive
G1, the growth of the dendrimer was pursued by treatment tool.[17] It is especially useful during the nucleophilic substi-
with six equivalents of the salt 2-Na. In this case also, the tution. Indeed, on going from the P(S)Cl2 end-groups (δ =
reaction is slow and again needs five days at 40 °C in THF 61.3 ppm) to the P(S)(OAr)2 end-groups (δ = 62.0 ppm), a
to go to completion. The nucleophilic substitution induces signal corresponding to the intermediate P(S)Cl(OAr) (δ =
a slight deshielding of the signal corresponding to the phos- 67 ppm) is always observed, and disappears when the reac-
1342
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 1340–1347

Phosphorus Dendrimers Containing Long, Conjugated Branches
FULL PAPER
Figure 2. π–π interactions between two molecules of 1-G1.
Figure 3. Short distances found in the crystal of 1-G1.
tion has gone to completion. Interestingly, the condensation step. However, the yields of isolated products are not quan-
reaction with the phosphorhydrazide 3 is also detectable by titative due to several washings carried out to eliminate the
31P NMR spectroscopy: it produces a slight deshielding (slight) excess of reagents used. The yields of isolated com-
from δ = 62.0 ppm to δ Ϸ 62.5 ppm for the phosphorus pounds after the condensation steps are always better than
that bears the cinnamaldehyde groups, despite the very long the yields after the nucleophilic substitution steps because
distance (9 bonds!) between these phosphorus centres and an excess of the salt 2-Na is used in order to accelerate the
1
the sites of reaction. Furthermore, at this step, H NMR reaction, and the total elimination of this excess by success-
spectroscopy shows the total disappearance of the signals ive washings also eliminates part of the dendrimer.
corresponding to the aldehydes. The signals corresponding
to the CH=CH linkages are not detected by 1H NMR spec-
troscopy due to overlap of signals. However, we have al-
ready shown for phosphorus dendrimers containing photo-
Conclusions
isomerisable azobenzene linkages as branches that dramatic
We have reported the synthesis of a new family of dendri-
changes occur in the 31P NMR spectra upon isomeriza- mers made of very long branches containing 11 bonds be-
tion;[18] this phenomenon is not observed for compounds 1- tween each branching point. The determination of the
Gn, thus the trans configuration is retained.
structure of the first generation by X-ray diffraction shows
All reactions are quantitative on the crude products: that these long branches are relatively planar due to their
NMR monitoring shows the total disappearance of the sig- conjugation, thereby providing a semi-rigid skeleton to the
nals corresponding to the dendrimer end-groups at each dendrimers. To the best of our knowledge the length of each
Eur. J. Org. Chem. 2005, 1340–1347
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1343

A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
Scheme 2.
1
and SiMe4 for H and 13C NMR spectroscopy. The assignment of
13C NMR signals was performed using Jmod, two dimensional
HMBC, and HMQC, Broad Band or CW 31P decoupling experi-
ments where necessary. The numbering scheme used for the NMR
assignments is shown in Figure 4.
arm (12 Å) is the largest value determined by X-ray diffrac-
tion for any type of regular dendrimer. The synthesis has
been carried out up to the fifth generation, thus demon-
strating the viability of the synthetic pathway up to high
generations. No steric hindrance is observed, and the syn-
thesis could have been pursued, although the lengthy nucle-
ophilic substitution process did not incite us to continue
the growth. The compounds obtained are large enough to
Dendrimer (1-G0Ј).First Method: Thiophosphoryl trichloride
(313 μL, 3.08 mmol) was added under argon to a solution of
cinnamaldehyde (1.65 g, 9.26 mmol, 3 equiv.) and Cs2CO3 (2.93 g,
possess all the properties of dendrimers, and work is in pro- 9.5 mmol, 4 equiv.) in anhydrous THF (10 mL). The suspension
was stirred for 3 d at room temp. The solution was half evaporated
and dichloromethane was added (10 mL). The solution was filtered
twice and the resulting orange solution was evaporated. The crude
solid was dissolved in THF and a large amount of pentane was
added, the suspension was vigorously stirred and the solvent was
removed. The solid was washed again with THF/pentane and then
with Et2O (two times) and finally with ethanol. Yield: 52%, pale-
yellow solid.
Second Method: Thiophosphoryl chloride (0.15 mL, 1.5 mmol) was
added to a heterogeneous solution of the sodium salt of 4-hydroxy-
3-methoxycinnamaldehyde (1 g, 5 mmol, obtained by reaction of
1 equiv. of NaH with 4-hydroxy-3-methoxycinnamaldehyde) in
THF. The resulting mixture was stirred for 5 d at 40 °C. The hetero-
geneous solution was then centrifuged for 30 min at 10 000 rpm.
gress to compare the properties of these new compounds
with those of dendrimers having shorter branches.
Experimental Section
General Remarks: All manipulations were carried out with stan-
dard high-vacuum and dry-argon techniques. The solvents were
freshly dried and distilled (THF and diethyl ether over sodium/
benzophenone; pentane and CH2Cl2 over phosphorus pentoxide;
toluene over sodium). All experiments were protected against light
1
by aluminium foils. H, 13C and 31P NMR spectra were recorded
with Bruker AC 200, AC 250, DPX 300 or AMX 400 spectrome-
ters. References for NMR chemical shifts are 85% H3PO4 for 31P
Figure 4. Numbering used for the NMR spectra.
1344
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 1340–1347

Phosphorus Dendrimers Containing Long, Conjugated Branches
FULL PAPER
The solution was recovered, evaporated to dryness, and washed
three times with THF/pentane (1:5). Yield: 63%, pale-yellow pow-
der, m.p. 196–198 °C. H NMR (CDCl3, 200.1 MHz): δ = 3.87 (s,
(s, P1) ppm. IR (KBr): νC=O = 1676 cm–1. C93H90N6O24P4S4 (1928):
calcd. C 57.94, H 4.71, N 4.36; found C 58.06, H 4.77, N 4.31.
1
Dendrimer 1-G2: Yield: 85%, pale-yellow powder. 1H NMR
3
3
9 H, O-Me0), 6.66 (dd, JH,Htrans = 15.9, JH,H = 7.6 Hz, 3 H, H-
3
(CDCl3, 250.1 MHz): δ = 3.44 (d, JH,P = 14.0 Hz, 27 H, N-Me0,
8
3
5
C0 ), 7.15 (s, 3 H, H-C0 ), 7.17 (d, 3JH,H = 8 Hz, 3 H, H-C0 ), 7.44
N-Me1), 3.83 (s, 9 H, O-Me0), 3.86 (s, 18 H, O-Me1), 7.00 (m, 36
3
7
3
4
(d, JH,Htrans = 15.9 Hz, 3 H, H-C0 ), 7.55 (dd, JH,H = 8, JH,P
=
H, H-C=), 7.29 (d, 3JH,H = 8.2 Hz, 6 H, H-C1 ), 7.52 (m, 12 H, H-
6
6
3
9
1.5 Hz, 3 H, H-C0 ), 9.69 (d, JH,H = 7.6 Hz, 3 H, H-C0 ) ppm.
2
C=) ppm. 13C{1H} NMR (CDCl3, 62.9 MHz): δ = 32.1 (d, JC,P
=
13C{1H} NMR (CDCl3, 62.9 MHz): δ = 56.1 (s, O-Me0), 111.8 (s,
2
10.5 Hz, N-Me1), 32.8 (d, JC,P = 9.8 Hz, N-Me0), 56.1 (s, O-Me0),
56.2 (s, O-Me1), 110.0 (s, C0 ), 110.2 (s, C1 ), 120.0 (s, C0 ), 120.3
(s, C1 ), 122.4 (d, JC,P = 3.9 Hz, C0 ), 122.6 (d, JC,P = 4.0 Hz,
C1 ), 125.3 (s, C1 ), 126.6 (s, C0 ), 134.0 (s, C1 ), 134.6 (s, C0 ),
3
5
3
6
8
C0 ), 121.7 (s, C0 ), 122.9 (d, JC,P = 1 Hz, C0 ), 128.8 (s, C0 ),
3
3
5
4
2
1
7
2
132.4 (s, C0 ), 142.1 (d, JC,P = 7.8 Hz, C0 ), 151.6 (s, C0 , C0 ),
5
3
6
3
193.3 (s, C0 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ = 53.8
9
6
8
8
4
4
(s, P0) ppm. IR (KBr): νC=O = 1671 cm–1. C30H27O9PS (594.6):
7
7
2
1
136.3 (s, C0 ), 138.9 (s, C1 ), 140.6 (d, JC,P = 7.8 Hz, C0 ), 140.8
calcd. C 60.60, H 4.58; found C 60.68, H 4.61.
2
1
3
9
(d, JC,P = 7.8 Hz, C1 ), 141.5 (d, JC,P = 13.8 Hz, C0 ), 144.3 (d,
3JC,P = 14.0 Hz, C1 ), 151.3 (d, 3JC,P = 5.5 Hz, C0 ), 151.6 (d, 3JC,P
9
2
General Method for the Synthesis of Dendrimers with P(S)Cl2 End-
Groups (Series Gn) (n = 1–5): A solution of H2NNMeP(S)Cl2 (10%
excess) in CHCl3 was added at room temp. to a solution of den-
drimer 1-Gn–1Ј dissolved in a minimum amount of THF. The re-
sulting solution was stirred for 24 h at room temperature then evap-
orated to dryness, and the resulting powder was washed at least
three times with diethyl ether/pentane (1:5), to afford dendrimer 1-
Gn as a pale-yellow powder.
= 5.6 Hz, C1 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ = 54.8
2
(s, P0), 61.4 (s, P2), 62.7 (s, P1) ppm. C99H108Cl12N18O18P10S10
(2894): calcd. C 41.09, H 3.76, 8.71; found C 41.21, H 3.82, N 8.65.
Dendrimer 1-G2Ј: Yield: 81%, pale-yellow powder. 1H NMR
3
(CDCl3, 250.1 MHz): δ = 3.42 (d, JH,P = 10.3 Hz, 27 H, N-Me0,
N-Me1), 3.85 (br. s, 63 H, O-Me0, O-Me1, O-Me2), 6.63 (dd,
3
8
3JH,Htrans = 15.8, JH,H = 7.7 Hz, 12 H, H-C2 ), 6.70–7.60 (m, 102
3
9
General Method for the Synthesis of Dendrimers with CHO End-
Groups (Series GnЈ) (n = 1–5): The dendrimer 1-Gn dissolved in a
minimum amount of THF was added to a heterogeneous solution
of the sodium salt of 4-hydroxy-3-methoxycinnamaldehyde (10%
excess) in THF. The resulting mixture was stirred for 5 d at 40 °C.
The heterogeneous solution was centrifuged, and the solution was
recovered, evaporated to dryness, and washed three times with
THF/pentane (1:5).
H, H-C=), 9.67 (d, JH,H = 7.6 Hz,12 H, H-C2 ) ppm. 13C{1H}
NMR (CDCl3, 50.3 MHz): δ = 32.6 (d, JC,P = 12 Hz, N-Me0, N-
2
Me1), 55.8 (s, O-Me0), 55.9 (s, O-Me1), 56.0 (s, O-Me2), 109.8 (br.
3
3
3
5
5
5
s, C0 , C1 ), 111.6 (s, C2 ), 119.9 (br. s, C0 , C1 ), 121.6 (s, C2 ),
6
6
3
6
123.2 (br. s, C0 , C1 ), 123.7 (d, JC,P = 3.5 Hz, C2 ), 126.0 (br. s,
8
8
8
4
4
4
C0 , C1 ), 128.3 (s, C2 ), 131.8 (s, C2 ), 134.2 (br. s, C0 , C1 ), 136.5
7
7
1
1
9
9
(s, C0 , C1 ), 140.2 (br. s, C0 , C1 ), 141.8 (br. s, C0 , C1 ), 142.2 (d,
2JC,P = 7.3 Hz, C2 ), 151.2 (br. s, C0 , C1 ), 151.6 (d, 3JC,P = 5.9 Hz,
1
2
2
2
7
9
C2 ), 151.8 (s, C2 ), 193.3 (s, C2 ) ppm. 31P{1H} NMR (CDCl3,
81.01 MHz): δ = 54.7 (s, P0), 62.0 (s, P2), 62.5 (s, P1) ppm. IR
(KBr): νC=O = 1676 cm–1. C219H216N18O54P10S10 (4595): calcd. C
57.25, H 4.74, N 5.49; found C 57.33, H 4.81, N 5.41.
Dendrimer 1-G1: Yield: 90%, pale-yellow powder. Single crystals
suitable for X-ray diffraction were grown from a saturated acetoni-
trile solution at room temperature. 1H NMR (CDCl3, 200.1 MHz):
3
δ = 3.44 (d, JH,P = 13.9 Hz, 9 H, N-Me0), 3.87 (s, 9 H, O-Me0),
3
7
3
6.87 (d, JH,Htrans = 16.0 Hz, 3 H, H-C0 ), 7.00 (dd, JH,Htrans
=
Dendrimer 1-G3: Yield: 83%, pale-yellow powder. 1H NMR
3
8
3
3
16.0, JH,H = 8.0 Hz, 3 H, H-C0 ), 7.03 (d, JH,H = 8.4 Hz, 3 H, (CDCl3, 250.1 MHz): δ = 3.41 (br. d, JH,P = 11.5 Hz, 63 H, N-
5
3
4
H-C0 ), 7.11 (s, 3 H, H-C0 ), 7.50 (dd, 3JH,H = 8.4, JH,P = 1.7 Hz,
Me0, N-Me1, N-Me2), 3.85 (br. s, 63 H, O-Me0, O-Me1, O-Me2),
3 H, H-C0 ), 7.56 (dd, 3JH,H = 8, 4JH,P = 2.3 Hz, 3 H, H-C0 ) ppm.
6.80–7.60 (m, 126 H, H-C=) ppm. 13C{1H} NMR (CDCl3,
6
9
13C{1H} NMR (CDCl3, 62.9 MHz): δ = 32.1 (d, JC,P = 11.8 Hz, 62.9 MHz): δ = 32.1 (d, JC,P = 13.6 Hz, N-Me2), 32.8 (d, JC,P
=
2
2
2
3
5
N-Me0), 56.1 (s, O-Me0), 110.3 (s, C0 ), 120.2 (s, C0 ), 122.6 (d, 10.9 Hz, N-Me0, N-Me1), 56.2 (s, O-Me0, O-Me1, O-Me2), 110.0
3JC,P = 3.7 Hz, C0 ), 125.4 (s, C0 ), 134.1 (s, C0 ), 138.8 (s, C0 ),
(br. s, C0 , C1 ), 110.2 (s, C2 ), 120.0 (br. s, C0 , C1 ), 120.4 (s, C2 ),
6
8
4
7
3
3
3
5
5
5
1
9
6
6
6
8
8
8
140.6 (d, 2JC,P = 7.3 Hz, C0 ), 144.2 (d, 3JC,P = 19.6 Hz, C0 ), 151.3
122.6 (br. s, C0 , C1 , C2 ), 125.2 (s, C2 ), 126.4 (br. s, C0 , C1 ),
(d, 3JC,P = 5.8 Hz, C0 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): 133.8 (s, C2 ), 134.4 (br. s, C0 , C1 ), 136.3 (s, C0 , C1 ), 139.0 (s,
2
4
4
4
7
7
7
1
1
2
1
δ = 54.6 (s, P0), 61.3 (s, P1) ppm. C33H36Cl6N6O6P4S4 (1077.6): C2 ), 140.2 (br. s, C0 , C1 ), 140.7 (d, JC,P = 7.5 Hz, C2 ), 141.8
calcd. C 36.78, H 3.37, N 7.80; found C 36.82, H 3.39, N 7.76.
9
9
3
9
2
(br. s, C0 , C1 ), 144.4 (d, JC,P = 19.9 Hz, C2 ), 151.5 (br. s, C0 ,
C1 , C2 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ = 54.7 (s,
P0), 61.3 (s, P3), 62.4 (s, P1, P2) ppm. C231H252Cl24N42O42P22S22
(6527): calcd. 42.51, H 3.89, N 9.01; found C 42.66, H 3.95, N 8.94.
2
2
Dendrimer 1-G1Ј: Yield: 80%, pale-yellow powder, m.p. 165–
3
166 °C. 1H NMR (CDCl3, 250.1 MHz): δ = 3.42 (d, JH,P
=
10.5 Hz, 9 H, N-Me0), 3.83 (s, 9 H, O-Me0), 3.87 (s, 18 H, O-Me1),
3
3
8
6.64 (dd, JH,Htrans = 15.9, JH,H = 7.6 Hz, 6 H, H-C1 ), 6.81 (d,
Dendrimer 1-G3Ј: Yield: 65%, pale-yellow powder. 1H NMR
3JH,Htrans = 15.9 Hz, 3 H, H-C0 ), 7.00 (m, 6 H, H-C0 , H-C0 ), (CDCl3, 200.1 MHz): δ = 3.38 (br. d, JH,P = 11.9 Hz, 63 H, N-
7
8
5
3
3
3
3
7.08 (s, 3 H, H-C0 ), 7.12 (s, 6 H, H-C1 ), 7.13 (d, JH,H = 8.8 Hz,
Me0, N-Me1, N-Me2), 3.82 (br. s, 135 H, O-Me0, O-Me1, O-Me2,
5
3
4
6
3
6 H, H-C1 ), 7.36 (dd, JH,H = 8.8, JH,P = 1.7 Hz, 6 H, H-C1 ),
O-Me3), 6.50–7.60 (m, 246 H, H-C=), 9.63 (d, JH,H = 7.1 Hz, 24
3
7
3
9
7.41 (d, JH,Htrans = 15.9 Hz, 6 H, H-C1 ), 7.47 (dd, JH,H = 8.4,
H, H-C3 ) ppm. 13C{1H} NMR (CDCl3, 50.3 MHz): δ = 32.6 (d,
4JH,P = 1.6 Hz, 3 H, H-C0 ), 7.59 (dd, JH,H = 8.7, JH,P = 1.8 Hz,
2JC,P = 11.9 Hz, N-Me0, N-Me1, N-Me2), 55.7 (s, O-Me0), 55.8 (s,
6
3
4
3 H, H-C0 ), 9.67 (d, JH,H = 7.6 Hz, 6 H, H-C1 ) ppm. 13C{1H}
O-Me1), 55.9 (s, O-Me2), 56.0 (s, O-Me3), 109.8 (br. s, C0 , C1 ,
9
3
9
3
3
2
3
3
5
5
5
5
NMR (CDCl3, 62.9 MHz): δ = 32.8 (d, JC,P = 11.8 Hz, N-Me0), C2 ), 111.7 (s, C3 ), 119.9 (br. s, C0 , C1 , C2 ), 121.6 (s, C3 ), 122.3
3
3
6
6
6
3
6
56.0 (s, O-Me0), 56.2 (s, O-Me1), 110.0 (s, C0 ), 111.9 (s, C1 ), 119.9 (br. s, C0 , C1 , C2 ), 122.6 (d, JC,P = 4.0 Hz, C3 ), 126.0 (br. s,
(s, C0 ), 121.8 (s, C1 ), 122.5 (d, 3JC,P = 3.1 Hz, C0 ), 122.9 (d, 3JC,P C0 , C1 , C2 ), 128.3 (s, C3 ), 131.8 (s, C3 ), 134.1 (br. s, C0 , C1 ,
5
5
6
8
8
8
8
4
4
4
6
8
8
4
4
7
7
7
1
1
1
= 3.7 Hz, C1 ), 126.4 (s, C0 ), 128.5 (s, C1 ), 132.0 (s, C1 ), 134.6
C2 ), 136.5 (br. s, C0 , C1 , C2 ), 140.2 (br. s, C0 , C1 , C2 ), 141.7
(s, C0 ), 136.5 (s, C0 ), 140.3 (d, 2JC,P = 7.8 Hz, C0 ), 141.8 (d, 3JC,P (br. s, C0 , C1 , C2 ), 142.2 (d, JC,P = 7.5 Hz, C3 ), 151.3 (br. s,
4
7
1
9
9
9
2
1
9
2
1
3
2
2
2
3
2
7
= 15.3 Hz, C0 ), 142.3 (d, JC,P = 7.7 Hz, C1 ), 151.3 (d, JC,P
=
C0 , C1 , C2 ), 151.5 (d, JC,P = 4.8 Hz, C3 ), 151.8 (s, C3 ), 193.3
2
3
2
7
9
5.8 Hz, C0 ), 151.7 (d, JC,P = 6 Hz, C1 ), 151.9 (s, C1 ), 193.4 (s,
(s, C3 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ = 54.7 (s, P0),
C1 ) pm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ = 54.7 (s, P0), 62.0 61.9 (s, P3), 62.5 (br. s, P1, P2) ppm. IR (KBr): νC=O = 1676 cm–1.
9
Eur. J. Org. Chem. 2005, 1340–1347
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1345

A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
C471H468N42O114P22S22 (9928): calcd. C 56.98, H 4.75, N 5.93;
found C 57.07, H 4.82, N 5.87.
6
6
6
6
6
8
8
8
C0 , C1 , C2 , C3 ), 122.8 (br. s, C4 ), 126.2 (br. s, C0 , C1 , C2 ,
8
8
8
4
4
4
4
C3 , C4 ), 128.5 (s, C5 ), 132.0 (s, C5 ), 134.3 (br. s, C0 , C1 , C2 ,
4
4
7
7
7
7
7
1
C3 , C4 ), 136.7 (br. s, C0 , C1 , C2 , C3 , C4 ), 140.4 (br. s, C0 ,
Dendrimer 1-G4: Yield: 80%, pale-yellow powder. 1H NMR
(CDCl3, 250.1 MHz): δ = 3.40 (br. d, JH,P = 13 Hz, 135 H, N-
1
1
1
1
9
9
9
9
9
C1 , C2 , C3 , C4 ), 142.0 (br. s, C0 , C1 , C2 , C3 , C4 ), 142.4 (d,
3
1
3
2
2
2
2
2JC,P = 7.0 Hz, C5 ), 151.3 (br. d, JC,P = 5 Hz, C0 , C1 , C2 , C3 ,
Me0, N-Me1, N-Me2, N-Me3), 3.83 (br. s, 135 H, O-Me0, O-Me1,
C4 ), 151.5 (d, 3JC,P = 5 Hz, C5 ), 151.9 (s, C5 ), 193.4 (s, C5 ) ppm.
31P{1H} NMR (CDCl3, 81.0 MHz): δ = 54.9 (s, P0), 62.4 (s, P5),
63.2 (br. s, P1, P2, P3, P4). IR (KBr): νC=O = 1676 cm–1.
C1983H1980N186O474P94S94 (41 928): calcd. C 56.81, H 4.76, N 6.21;
found C 56.96, H 4.82, N 6.17.
2
2
7
9
O-Me2, O-Me3), 6.70–7.60 (m, 270 H, H-C=) ppm. 13C{1H} NMR
2
(CDCl3, 62.9 MHz): δ = 32.0 (d, JC,P = 13.1 Hz, N-Me3), 32.7 (d,
2JC,P = 11.5 Hz, N-Me0, N-Me1, N-Me2), 56.0 (s, O-Me0, O-Me1,
3
3
3
3
O-Me2, O-Me3), 109.7 (br. s, C0 , C1 , C2 ), 110.0 (s, C3 ), 119.9
5
5
5
5
6
6
6
6
(br. s, C0 , C1 , C2 ), 120.2 (s, C3 ), 122.4 (br. s, C0 , C1 , C2 , C3 ),
8
8
8
8
4
X-ray Crystallographic Study: Crystal structure information is
given in Table 3. Data were collected at low temperature on a IPDS
STOE diffractometer equipped with graphite-monochromated Mo-
Kα radiation (λ = 0.71073Å) and an Oxford Cryosystems Cryos-
tream Cooler Device. The final unit-cell parameters were obtained
by means of a least-squares refinement performed on a set of 8000
well-measured reflections; crystal decay was monitored during the
data collections, no significant fluctuations of intensities were ob-
served. The structure was solved by direct methods using SIR92,[19]
and refined by means of least-squares procedures on F using the
programs of the PC version of CRYSTALS.[20] Atomic scattering
factors were taken from the International tables for X-ray Crystal-
lography.[21] All final phosphorus, chlorine and sulfur atom posi-
tions were refined anisotropically. Hydrogen atoms were introduced
in calculated positions in the last refinements and were allocated
an overall refinable isotropic thermal parameter. A weighting
scheme of the form w = wЈ[1 – {(||Fo| – |Fc||)/6σ(Fo)}2]2 with wЈ =
1/ΣrArTr(X) with coefficients 1.44, 0.859 and 0.977 for a Chebychev
series for which X = Fc/Fc(max.) was used. CAMERON[22] was
used for the drawing. CCDC-249559 contains the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
125.0 (s, C3 ), 126.2 (br. s, C0 , C1 , C2 ), 133.7 (s, C3 ), 134.2 (br.
4
4
4
7
7
7
7
s, C0 , C1 , C2 ), 136.2 (br. s, C0 , C1 , C2 ), 138.8 (s, C3 ), 140.1
(br. d, 2JC,P = 8.0 Hz, C0 , C1 , C2 ), 140.5 (d, 2JC,P = 7.0 Hz, C3 ),
1
1
1
1
9
9
9
3
9
141.4 (br. m, C0 , C1 , C2 ), 144.2 (d, JC,P = 18.5 Hz, C3 ), 151.3
(br. d, JC,P = 4.5 Hz, C0 , C1 , C2 , C3 ) ppm. 31P{1H} NMR
(CDCl3, 81.01 MHz): δ = 54.7 (s, P0), 61.4 (s, P4), 62.9 (s, P3), 63.0
(s, P2), 63.1 (s, P1) ppm. C495H540Cl48N90O90P46S46 (13 792): calcd.
C 43.11, H 3.95, N 9.14; found C 43.28, H 4.02, N 9.06.
3
2
2
2
2
Dendrimer 1-G4Ј: Yield: 70%, pale-yellow powder. 1H NMR
(CDCl3, 250.1 MHz): δ = 3.38 (br. s, 135 H, N-Me0, N-Me1, N-
Me2, N-Me3), 3.84 (br. s, 279 H, O-Me0, O-Me1, O-Me2, O-Me3,
9
O-Me4), 6.50–7.60 (m, 510 H, H-C=), 9.64 (br. s, 48 H, H-C4 )
ppm. 13C{1H} NMR (CDCl3, 62.9 MHz): δ = 32.7 (d, JC,P
=
2
11.9 Hz, N-Me0, N-Me1, N-Me2, N-Me3), 56.1 (s, O-Me0, O-Me1,
3
3
3
3
O-Me2, O-Me3), 56.2 (s, O-Me4), 110.0 (br. s, C0 , C1 , C2 , C3 ),
3
5
5
5
5
5
111.9 (s, C4 ), 120.0 (br. s, C0 , C1 , C2 , C3 ), 121.8 (s, C4 ), 122.6
6
6
6
6
6
8
8
(br. s, C0 , C1 , C2 , C3 ), 122.8 (br. s, C4 ), 126.2 (br. s, C0 , C1 ,
8
8
8
4
4
4
4
C2 , C3 ), 128.5 (s, C4 ), 132.0 (s, C4 ), 134.3 (br. s, C0 , C1 , C2 ,
4
7
7
7
7
1
1
1
C3 ), 136.5 (br. s, C0 , C1 , C2 , C3 ), 140.3 (br. s, C0 , C1 , C2 ,
1
9
9
9
9
1
C3 ), 141.8 (br. s, C0 , C1 , C2 , C3 ), 142.3 (d, 2JC,P = 7.2 Hz, C4 ),
3
2
2
2
2
3
151.3 (br. d, JC,P = 5.4 Hz, C0 , C1 , C2 , C3 ), 151.5 (d, JC,P
=
2
7
9
4.8 Hz, C4 ), 151.9 (s, C4 ), 193.5 (s, C4 ) ppm. 31P{1H} NMR
(CDCl3, 101.2 MHz): δ = 54.9 (s, P0), 62.4 (s, P4), 63.2 (br. s, P1,
P2, P3) ppm. IR (KBr): νC=O = 1676 cm–1. C975H972N90O234P46S46
(20 595): calcd. C 56.86, H 4.76, N 6.12; found C 56.99, H 4.83, N
6.05.
Table 3. Crystal data, data collection, and structure refinement.
Empirical formula
Molecular mass
C35H39Cl6N7O6P4S4
1118.61
Wavelength
Crystal system, space group
Unit cell dimensions
0.71073 Å
triclinic, P1
a = 12.865(1) Å
b = 13.974(2) Å
c = 14.279(2) Å
α = 94.10(1)°
Dendrimer 1-G5: Yield: 79%, pale-yellow powder. 1H NMR
(CDCl3, 200.1 MHz): δ = 3.40 (br. s, 279 H, N-Me0, N-Me1, N-
Me2, N-Me3, N-Me4), 3.82 (br. s, 279 H, O-Me0, O-Me1, O-Me2,
O-Me3, O-Me4), 6.70–7.60 (m, 558 H, H-C=) ppm. 13C{1H} NMR
¯
2
(CDCl3, 50.3 MHz): δ = 32.9 (d, JC,P = 13.0 Hz, N-Me4), 32.6 (d,
2JC,P = 11.7 Hz, N-Me0, N-Me1, N-Me2, N-Me3), 56.0 (s, O-Me0,
β = 97.34(1)°
3
3
3
3
γ = 98.08(1)°
O-Me1, O-Me2, O-Me3, O-Me4), 109.8 (br. s, C0 , C1 , C2 , C3 ),
2510.2(5) Å3
3
5
5
5
5
5
Volume
110.0 (s, C4 ), 119.9 (br. s, C0 , C1 , C2 , C3 ), 120.2 (s, C4 ), 122.4
Z, calculated density
Absorption coefficient
F000
2, 1.48
6
6
6
6
6
8
8
8
(br. s, C0 , C1 , C2 , C3 , C4 ), 125.0 (s, C4 ), 126.2 (br. s, C0 , C1 ,
0.685 mm–1
8
8
4
4
4
4
4
C2 , C3 ), 133.7 (s, C4 ), 134.2 (br. s, C0 , C1 , C2 , C3 ), 136.1 (br.
1144
7
7
7
7
7
2
s, C0 , C1 , C2 , C3 ), 138.8 (s, C4 ), 140.1 (br. d, JC,P = 8.0 Hz,
Crystal size
0.05 × 0.25 × 0.30 mm
pale-yellow plate
2.16–26.19°
–15 Յ h Յ 15
–17 Յ k Յ 17
–17 Յ l Յ 17
24992/9244 [R(int) = 0.049]
Full matrix least-squares on F
3339/0/320
C0 , C1 , C2 , C3 ), 140.5 (d, 2JC,P = 7.0 Hz, C4 ), 141.5 (br. m, C0 ,
1
1
1
1
1
9
Crystal colour and form
θ range for data collection
Index ranges
9
9
9
3
9
2
C1 , C2 , C3 ), 144.2 (d, JC,P = 18.6 Hz, C4 ), 151.3 (br. s, C0 ,
C1 , C2 , C3 , C4 ) ppm. 31P{1H} NMR (CDCl3, 81.01 MHz): δ
= 54.7 (s, P0), 61.4 (s, P5), 63.0 (s, P4), 63.1 (s, P1, P2, P3) ppm.
C1023H1116Cl96N186O186P94S94 (28 322): calcd. C 43.38, H 3.97, N
9.20; found C 43.46, H 4.02, N 9.14.
2
2
2
2
Reflections collected/unique
Refinement method
Data/restraints/parameters
Goodness of fit on F
Dendrimer 1-G5Ј: Yield: 63%, pale-yellow powder. 1H NMR
3
(CDCl3, 250.1 MHz): δ = 3.40 (br. d, JH,P = 9.5 Hz, 279 H, N-
1.124
Final R indices [I Ͼ 2σ(I)]
Largest diff. peak and hole
R1 = 0.0700, wR2 = 0.0726
Me0, N-Me1, N-Me2, N-Me3, N-Me4), 3.85 (br. s, 567 H, O-Me0,
O-Me1, O-Me2, O-Me3, O-Me4, O-Me5), 6.50–7.60 (m, 1038 H, H-
(0.79 and –0.59) eÅ–3
3
9
C=), 9.66 (br. d, JH,H = 5 Hz, 96 H, H-C5 ). 13C{1H} NMR
2
(CDCl3, 62.9 MHz): δ = 32.7 (d, JC,P = 11.8 Hz, N-Me0, N-Me1,
N-Me2, N-Me3, N-Me4), 56.1 (s, O-Me0, O-Me1, O-Me2, O-Me3,
Acknowledgments
3
3
3
3
3
O-Me4), 56.2 (s, O-Me5), 110.0 (br. s, C0 , C1 , C2 , C3 , C4 ), 111.9
3
5
5
5
5
5
(s, C5 ), 120.0 (br. s, C0 , C1 , C2 , C3 ), 121.8 (s, C4 ), 122.6 (br. s,
Thanks are due to the CNRS for financial support.
1346
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 1340–1347

Phosphorus Dendrimers Containing Long, Conjugated Branches
FULL PAPER
[14] a) G. J. de A. A. Soler-Illia, L. Rozes, M. K. Boggiano, C. San-
chez, C. O. Turrin, A. M. Caminade, J. P. Majoral, Angew.
Chem. 2000, 112, 4420–4424; Angew. Chem. Int. Ed. 2000, 39,
4249–4254; b) C. Marmillon, F. Gauffre, T. Gulik-Krzywicki,
C. Loup, A. M. Caminade, J. P. Majoral, J. P. Vors, E. Rump,
Angew. Chem. 2001, 113, 2696–2699; Angew. Chem. Int. Ed.
2001, 40, 2626–2629; c) A. M. Caminade, J. P. Majoral, Acc.
Chem. Res. 2004, 37, 341–348.
[15] a) V. Maraval, R. Laurent, A. M. Caminade, J. P. Majoral, Or-
ganometallics 2000, 19, 4025–4029; b) A. M. Caminade, V. Ma-
raval, R. Laurent, J. P. Majoral, Current Org. Chem. 2002, 6,
739–774.
[16] a) C. Loup, M. A. Zanta, A. M. Caminade, J. P. Majoral, B.
Meunier, Chem. Eur. J. 1999, 5, 3644–3650; b) M. Maszewska,
J. Leclaire, M. Cieslak, B. Nawrot, A. Okruszek, A. M. Camin-
ade, J. P. Majoral, Oligonucleotides 2003, 13, 193–205; c) V.
Le Berre, E. Trevisiol, A. Dagkessamanskaia, S. Sokol, A. M.
Caminade, J. P. Majoral, B. Meunier, J. François, Nucleic Acid
Res. 2003, 31, e88/1–e88/8; d) J. Solassol, C. Crozet, V. Perrier,
J. Leclaire, F. Béranger, A. M. Caminade, B. Meunier, D. Dor-
mon, J. P. Majoral, S. Lehmann, J. Gen. Virol. 2004, 85, 1791–
1799.
[1]
[2]
Dendrimers and dendrons. Concepts, syntheses, applications
(Eds.: G. R. Newkome, C. N. Moorefield, F. Vögtle), Wiley-
VCH, Weinheim, 2001.
Dendrimers and Other Dendritic Polymers (Eds.: J. M. J.
Fréchet, D. A. Tomalia), John Wiley & Sons, Chichester, 2001.
J. P. Majoral, A. M. Caminade, Chem. Rev. 1999, 99, 845–880.
B. J. Bauer, E. J. Amis, in Dendrimers and Other Dendritic Poly-
mers (Eds.: J. M. J. Fréchet, D. A. Tomalia), John Wiley &
Sons, Chichester, 2001, chapter 11, p. 255.
D. A. Tomalia, H. Baker, J. Dewald, M. Hall, G. Kallos, S.
Martin, J. Roeck, J. Ryder, P. Smith, Polymer J. (Tokyo) 1985,
17, 117–132.
a) E. Buhleier, W. Wehner, F. Vögtle, Synthesis 1978, 155–158;
b) C. Wörner, R. Mülhaupt, Angew. Chem. 1993, 105, 1367–
1370; Angew. Chem. Int. Ed. Engl. 1993, 32, 1306–1308; c)
E. M. M. de Brabander van den Berg, E. W. Meijer, Angew.
Chem. 1993, 105, 1370–1372; Angew. Chem. Int. Ed. Engl. 1993,
32, 1308–1311.
[3]
[4]
[5]
[6]
[7] a) E. A. Rebrov, A. M. Muzafarov, V. S. Papkov, A. A. Zhad-
anov, Dokl. Akad. Nauk. SSSR 1989, 309, 376–380; b) H. Uch-
ida, Y. Kabe, K. Yoshino, A. Kawamata, T. Tsumuraya, S. Ma- [17] a) C. Galliot, C. Larré, A. M. Caminade, J. P. Majoral, Science
samune, J. Am. Chem. Soc. 1990, 112, 7077–7079.
[8] G. R. Newkome, Z. Q. Yao, G. R. Baker, V. K. Gupta, J. Org.
Chem. 1985, 50, 2003–2004.
1997, 277, 1981–1984; b) C. Larré, D. Bressolles, C. Turrin, B.
Donnadieu, A. M. Caminade, J. P. Majoral, J. Am. Chem. Soc.
1998, 120, 13070–13082; c) L. Brauge, G. Magro, A. M. Cami-
nade, J. P. Majoral, J. Am. Chem. Soc. 2001, 123, 6698–6699;
correction: J. Am. Chem. Soc. 2001, 123, 8446; d) J. Leclaire,
Y. Coppel, A. M. Caminade, J. P. Majoral, J. Am. Chem. Soc.
2004, 126, 2304–2305.
[9] C. J. Hawker, J. M. J. Fréchet, J. Am. Chem. Soc. 1990, 112,
7638–7647.
[10] F. Morgenroth, C. Kübel, K. Müllen, J. Mater. Chem. 1997, 7,
1207–1211.
[11] a) N. Launay, A. M. Caminade, R. Lahana, J. P. Majoral, An-
gew. Chem. 1994, 106, 1682–1684; Angew. Chem. Int. Ed. Engl.
1994, 33, 1589–1592; b) N. Launay, A. M. Caminade, J. P. Ma-
joral, J. Am. Chem. Soc. 1995, 117, 3282–3283.
[12] M. L. Lartigue, B. Donnadieu, C. Galliot, A. M. Caminade,
J. P. Majoral, J. P. Fayet, Macromolecules 1997, 30, 7335–7337.
[13] a) B. Miksa, S. Slomkowski, M. M. Chehimi, M. Delamar, J. P.
Majoral, A. M. Caminade, Colloid Polym. Sci. 1999, 277, 58–
[18] R. M. Sebastian, J. C. Blais, A. M. Caminade, J. P. Majoral,
Chem. Eur. J. 2002, 8, 2172–2183.
[19] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 1993, 26, 343–350.
[20] P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout, D. J.
Watkin, J. Appl. Crystallogr. 2003, 36, 1487.
[21] International Tables for X-ray Crystallography, Kynoch press,
Birmingham, England, 1974, vol. IV.
65; b) F. Le Derf, E. Levillain, A. Gorgues, M. Sallé, R. M. [22] D. J. Watkin, C· K. Prout, L. J. Pearce CAMERON, Chemical
Sebastian, A. M.Caminade, J. P. Majoral, Angew. Chem. 2001,
113, 230–233; Angew. Chem. Int. Ed. 2001, 40, 224–227.
Crystallography Laboratory, Oxford, UK, 1996.
Received: September 24, 2004
Eur. J. Org. Chem. 2005, 1340–1347
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1347