Phosphorus-containing dendrimers. Easy access to new multi-difunctionalized macromolecules

Article abstract of DOI:10.1021/jo960045b

Phosphorus-containing dendrimers 1-[G′₁]-1-[G′₄] (generation 1 to generation 4) possessing terminal aldehyde groups reacted with a variety of hydrazino compounds. Addition of hydrazine itself to 1-[G′₁]- 1-[G′₄]

Full text of DOI:10.1021/jo960045b

J . Org. Chem. 1996, 61, 3799-3805
3799
P h osp h or u s-Con ta in in g Den d r im er s. Ea sy Access to New
Mu lti-Difu n ction a lized Ma cr om olecu les
Nathalie Launay, Michael Slany, Anne-Marie Caminade, and J ean Pierre Majoral*
Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne 31077 Toulouse Ce´dex, France
Received J anuary 4, 1996X
Phosphorus-containing dendrimers 1-[G′1]-1-[G′4] (generation 1 to generation 4) possessing
terminal aldehyde groups reacted with a variety of hydrazino compounds. Addition of hydrazine
itself to 1-[G′1]-1-[G′4] afforded the corresponding dendrimers 2-[G1]-2-[G4] with hydrazono groups
at the periphery. Addition of methylhydrazine to 1-[G′1], 1-[G′4] gave the dendrimers 3-[G1], 3-[G4].
A Schiff reaction between 1-[G′1]-1-[G′4] and 1-amino-4-(2-hydroxyethyl)piperazine led to
dendrimers 5-[G1]-5-[G4] possessing up to 48 alcohol chain ends. Treatment of 1-[G′1], 1-[G′3]
with fluorenone hydrazone gave rise to macromolecules 7-[G1], 7-[G3] while the reaction of 1-[G′1],
1-[G′2], 1-[G′4] with 4-aminobenzo-15-crown-5 afforded the macromolecules 9-[G1], 9-[G2], 9-[G4]
in which up to 48 crown ether units are anchored on the surface. Wittig reactions between 1-[G′1]-
1-[G′4] with (acetylmethylene)triphenylphosphorane (10) or (cyanomethylene)triphenylphosphorane
(12) allowed the formation of dendrimers 11-[G1]-11-[G4] or 13-[G1], 13-[G4] with R,â unsaturated
ketones or cinnamonitrile units, respectively, on the surface. Disubstitution of terminal P(S)Cl2
groups of dendrimers 1-[G1]-1-[G7] with allylamine, propargylamine, or N-(trimethylsilyl)imidazole
easily occurred to give macromolecules 14-[G1]-14-[G7], 15-[G1], 15-[G4], 16-[G1], 16-[G4].
When a new field of research in chemistry is particu-
larly appealing, a number of assumptions concerning
properties and applications of structures resulting from
this new area are postulated but need to be checked
before going further on investigations. Dendrimer chem-
istry, a relatively recent branch of polymer chemistry,
obeys this observation.1 Among all the expected proper-
ties of these three-dimensional globular compounds, those
related to the reactivity of the peripheral functionalities
are often cited: the presence of a large number of free
chain ends should offer perspectives to develop all the
facets of chemistry (organic, inorganic, organometallic...)
on the surface of these macromolecules.
Surprisingly very little is known about surface reactiv-
ity2 of dendrimers even if several reports claim how
useful such a reactivity might be.
Therefore a part of the work within our research group
is targeted toward this goal. As an extension of some of
our previous studies3 we now propose to demonstrate
hereafter that chain end functionalities such as aldehyde
moieties or phosphorus-chlorine bonds of phosphorus-
containing dendrimers 1-[G′1]-1-[G′4] (generation 1 to
generation 4, aldehyde functions) or 1-[G1]-1-[G7] (gen-
eration 1 to generation 7, P-Cl functions), respectively,
are as reactive as monomer species i.e. RCHO or RP(X)-
Cl2 (X ) S, O). As a consequence a large number of multi-
difunctionalized dendrimers can be prepared; up to now
only a few species of this type were already reported.4
Resu lts a n d Discu ssion
Dendrimers 1-[G1]-1-[G7] or 1-[G′1]-1-[G′4], with
either terminal P-Cl bonds or terminal aldehyde groups,3a
were prepared by the reiteration of a two-step sequence:
treatment of halogenated phosphane sulfide with the
sodium salt of 4-hydroxybenzaldehyde followed by the
reaction of the resulting polyaldehyde with dichloro-
(methylhydrazino) sulfide (Scheme 1). The behavior of
these macromolecules toward different reagents was
examined in order to determine the influence of the size
of these polymers.
Rea ctivity of Ald eh yd e Ch a in En d s. Two well
known reactions involving aldehydes were investigated:
Schiff reactions and Wittig reactions. Schiff reactions
were performed with hydrazine, methylhydrazine, fluo-
renone hydrazone, and 1-amino-4-(2-hydroxyethyl)pip-
erazine in order to anchor at the periphery of dendrimers,
amino, fluorenone, or alcohol groups, respectively, while
Schiff reaction was also attempted with 4-aminobenzo-
15-crown-5 in order to cover the surface of dendrimers
with a large number of crown-ether units.
X Abstract published in Advance ACS Abstracts, May 1, 1996.
(1) Reviews: (a) Tomalia, D. A.; Naylor, A. M.; Goddart, W. A., III.
Angew. Chem., Int. Ed. Engl. 1990, 29, 138. (b) Mekelburger, H. B.;
J aworek, W.; Vo¨gtle, F. Angew. Chem., Int. Ed. Engl. 1992, 31, 1571.
(c) Tomalia, D. A.; Durst, H. D. in Topics in Current Chemistry, vol.
165; Supramolecular Chemistry 1: Directed Synthesis and Molecular
Recognition; Weber, E., Ed.; Springer Verlag: Berlin, Heidelberg, 1993;
pp 193-313. (d) Ottaviani, M. F.; Bossmann, S.; Turro, N. J .; Tomalia,
D. A. J . Am. Chem. Soc. 1994, 116, 661. (e) Fre´chet, J . M. J . Science
1994, 263, 1710. (f) Issberner, J .; Moors, R.; Vo¨gtle, F. Angew. Chem.
1994, 106, 2507; Angew. Chem. Int. Ed. Engl. 1994, 33, 2413. (g)
Moorefield, C. N.; Newkome, G. R. In Advances in Dendritic Molecules;
Newkome, G. R., Ed.; J AI Press: Greenwich CT, 1994; Vol. 1, p 1.
(2) See for example (a) J ansen, J . F. G. A.; De Brabander van der
Berg, E. M. M.; Meijer, E. W. Science 1994, 32, 1226. (b) Lee, J . J .;
Ford, W. T.; Moore, J . A.; Li, Y. F. Macromolecules 1994, 27, 4632. (c)
Van der Made, A. W.; Van Leeuwen, P. W. N. M. J . Chem. Soc., Chem.
Commun. 1992, 1400. (d) Knapen, J . W. J .; Van der Made, A. W.; De
Wilde, J . C.; van Leeuwen, P. W. N. M.; Wijkens, P.; Grove, D. M.;
van Koten, G. Nature 1994, 372, 659.
Treatment of a chloroform solution of 1-[G′1], 1-[G′2],
1-[G′3], or 1-[G′4] with a large excess of hydrazine at room
(4) See for example: (a) Tomalia, D. A.; Baker, H.; Dewald, H.; Hall,
M.; Kallos, C.; Martin, S.; Roeck, J .; Ryder, J .; Smith, P. Polymer J .
1985, 17, 117. (b) Tomalia, D. A.; Baker, H.; Dewald, J .; Hall, M.;
Kallos, C.; Martin, S.; Roeck, J .; Ryder, J .; Smith, P. Macromolecules
1986, 19, 2466. (c) Meltzer, A. D.; Tinell, D. A.; J ones, A. A.; Inglefield,
D.; Hedstrand, M.; Tomalia, D. A. Macromolecules 1992, 25, 4541. (d)
Tomalia, D. A. Top. Curr. Chem. 1993, 165, 193. (e) Hawker, C. J .;
Fre´chet, J . M. J . Macromolecules 1990, 23, 4726. (f) Wooley, K. L.;
Hawker, C. J .; Fre´chet, J . M. J . J . Am. Chem. Soc. 1993, 115, 11496.
(g) Hawker, C. J .; Wooley, K. L.; Fre´chet, J . M. J . J . Chem. Soc. Perkin
Trans 1 1993, 1287.
(3) (a) Launay, N.; Caminade, A.-M.; Lahana, R.; Majoral, J .-P.
Angew. Chem., Int. Ed. Engl. 1994, 33, 1589. (b) Launay, N.;
Caminade, A.-M.; Majoral, J .-P. J . Am. Chem. Soc. 1995, 117, 3282.
(c) Galliot, C.; Pre´vote´, D.; Caminade, A.-M.; Majoral, J .-P. J . Am.
Chem. Soc. 1995, 117, 5470. (d) Slany, M.; Bardaji, M.; Casanove, M.
J .; Caminade, A.-M.; Majoral, J .-P.; Chaudret, D. J . Am. Chem. Soc.
1995, 117, 9764.
S0022-3263(96)00045-X CCC: $12.00 © 1996 American Chemical Society

3800 J . Org. Chem., Vol. 61, No. 11, 1996
Launay et al.
Sch em e 1
compounds 3-[G1], 5-[G1], 7-[G1]). It is quite likely that
all the hydrazono fragments present a trans configura-
tion by analogy with a variety of derivatives possessing
such a linkage and characterized by X-ray diffraction
studies.5
Therefore Schiff reactions allowed us to graft easily on
the surface of dendrimers NH2, N(CH3)H, or OH groups
which potentially are new anchoring moieties extending
the possible applications of these macromolecules.
Of interest was also the reaction of 1-[G′1], 1-[G′2],
1-[G′4] with 4-aminobenzo-15-crown-5 8 leading to den-
drimers 9-[G1], 9-[G2], 9-[G4] possessing from 6 to 48
crown ether units on the surface (Scheme 2). Formation
of 9-[G1] necessitated one week of stirring in refluxing
THF while that of 9-[G4] (Scheme 3) necessitated three
weeks in the same experimental conditions! Here once
again steric hindrance played a key role but did not
prevent the reactions from going to completion.
None of the 1H and 13C NMR or IR spectra of com-
pounds 9-[G1], 9-[G2], 9-[G4] exhibited any signal that
could be attributed to unreacted carbonyl functions. 1H
or 13C NMR spectra showed singlets at 8.4 ppm (HCdNC)
or 156.5 ppm (HCdNC) due to the protons and carbons,
respectively, of the imine functions. Elemental analysis
confirmed the structure of all these compounds as well
as mass spectrometry (fast atom bombardment) for 9-[G1]
(m/z: 3013 [M + 1]+).
Some features of interest can be mentioned for den-
drimers 9-[G1], 9-[G2], 9-[G4]. First, terminal crown
ethers acted as shields against hydrolysis of imine
functions. Indeed no hydrolysis was observed for ex-
ample after stirring a THF/water (80/20) solution of
9-[G4] for 48 h at room temperature.
Secondly a preliminary study concerning the complex-
ation properties of these compounds showed that treat-
ment of 9-[G2] possessing 12 crown ether units with 12
equiv of sodium tetraphenylborate led after workup to a
white powder insoluble in common organic solvents and
in water. Elemental analysis of this powder showed that
the Na/P ratio is 12/10, thus demonstrating that the
twelve sodium cations are trapped by the dendrimer
9-[G2]. Nevertheless experiments have to be done to
confirm this observation and to extend this study in
dendrimers 9-[G1] and 9-[G4].
Wittig Rea ction s. Dendrimers 1-[G′1]-1-[G′4] were
reacted with (acetylmethylene)triphenylphosphorane (10)
for 48 h in refluxing THF. The new dendrimers 11-[G1]-
11-[G4] (Scheme 4) were isolated in high yields and
characterized by NMR, IR, elemental analysis, and mass
spectrometry for 11-[G1] (FAB, m/z: 1663 [M + 1]+).
Reactions were monitored by 31P NMR which allow to
observe the disappearance of the singlet due to 10 (δ 31P
) 14.3 ppm) on behalf of that of triphenylphosphine oxide
at 23.1 ppm and the deshielding of the signal due to
terminal P-(OC6H4CHdCHCOCH3)2 fragments in com-
parison with that of terminal P-OC6H4CHO groups. (δ
) 60.4 ppm for 1-[G′1]-1-[G′4]; 61.6 ppm for 11-[G1]-
11-[G4]). 1H NMR spectra clearly established a trans
temperature for 2 h gave rise to the dendrimers 2-[G1]-
2-[G4] in quantitative yields (Scheme 2). Reactions were
monitored by 31P NMR which show the disappearance of
the signal due to the external thiophosphoryl groups (δ
31P ) 60.4 ppm) on behalf of a new signal at 62.2 ppm
corresponding to the terminal (S)P(OC6H4CHdNNH2)2
groups of dendrimers 2-[G1]-2-[G4]. Formation of the
hydrazono moieties was corroborated by the absence of
signals due to aldehyde groups in 1H and 13C NMR as
1
well as in IR spectroscopies. Moreover H and 13C NMR
confirmed the presence of hydrazono CHdNNH2 protons
(δH ) 7.4 ppm) and carbon (δCH ) 141.6 ppm) while mass
spectrometry (fast atom bombardment) indicated that the
six condensation reactions took place (MS m/z: 1507 [M
+ 1]+) for 2-[G1].
The same reactions were conducted with 1-[G′1] or
1-[G′4] and monomethylhydrazine leading in high yield
to dendrimers 3-[G1] or 3-[G4]: here also, reactions
needed 2 h to go to completion. In contrast the reaction
of 1-[G′1]-1-[G′4] with 1-amino-4-(2-hydroxyethyl)pip-
erazine (4) necessitated two days in refluxing chloroform
and led to 5[G1]-5-[G4]. A deshielding effect of ≈2 ppm
was detected in 31P NMR when moving from terminal
aldehyde groups (δ 31P ) 60.4 ppm) to terminal hydra-
zono groups (δ 31P ) 62.4 ppm); furthermore a signal
corresponding to the condensation of one of the two
aldehydic fragments of each terminal (S)P-(OC6H4CHO)2
moieties with 4 was observed at 61.1 ppm. Such a signal
further disappeared on behalf of that at 62.4 ppm. Such
a phenomenon also occurred when 1-[G′1] or 1-[G′3] were
treated with the fluorenone hydrazone 6 to give 7-[G1]
or 7-[G3]: reactions are extremely slow (one week for
1-[G′1], 3 weeks for 1-[G′3], room temperature) and
monocondensation (δ 31P ) 60.7 ppm) and then dicon-
densation (δ 31P ) 61.6 ppm) can be easily detected.
Steric hindrance introduced by the fluorenone groups
probably explains why the reaction is so slow and why
attempts to fully substituted 1-[G′4] with 6 failed up to
now. Compounds 3-[G1], 3-[G4], 5-[G1]-5[G4], 7-[G1],
(5) (a) Badri, M.; Majoral, J .-P.; Caminade, A.-M.; Delmas, M.; Gaset,
A.; Gorgues, A.; J aud, J . J . Am. Chem. Soc. 1990, 112, 5618. (b) Gonce,
F.; Caminade, A.-M.; Majoral, J .-P.; J aud, J ., Vignaux, J . Bull. Soc.
Chim. Fr. 1992, 129, 237. (c) Oussaid, B.; Garrigues, B.; J aud, J .;
Caminade, A.-M.; Majoral, J .-P. J . Org. Chem. 1993, 58, 4500. (d)
Colombo-Khater, D.; He, Z.; Caminade, A.-M.; Dahan, F.; Kraemer,
R.; Majoral, J .-P. Synthesis 1993, 1145. (e) Colombo-Khater, D.;
Caminade, A.-M.; Raynaud, B.; J aud, J .; Majoral, J .-P. Bull. Soc. Chim.
Fr. 1994, 131, 733. (f) Mitjaville, J .; Caminade, A.-M.; Daran, J .-C.;
Donnadieu, B.; Majoral, J .-P. J . Am. Chem. Chem. Soc. 1995, 117, 1712.
1
7-[G3] were fully characterized by H and 13C NMR as
well as by elemental analysis and mass spectra (for

Phosphorus-Containing Dendrimers
J . Org. Chem., Vol. 61, No. 11, 1996 3801
Sch em e 2
Sch em e 3
3
configuration for the olefinic chain ends (CHdCH, J HH
) 16.3 Hz). IR spectra display two strong absorptions
in the carbonyl stretching region, presumably due to s-cis
and s-trans conformations of the HCdCHCdO frag-
ments.6
(cyanomethylene)triphenylphosphorane 12. Reactions of
12 with 1-[G′1] and 1-[G′4] were achieved in 12 h in
refluxing THF and led in 58-62% yield to the new
macromolecules 13-[G1] or 13-[G4] possessing either 6
or 48 terminal cinnamonitrile type groups (Scheme 4).
Contrary to what was observed for the reactions of
1-[G′1]-1-[G′4] with the phosphorus ylide 10, a mixture
of trans/cis isomers in a 4/1 ratio was obtained for 13-
Therefore the Wittig reaction allowed us to anchor up
to 48 R,â unsaturated ketones on the surface of our
dendrimers. A similar experiment can be done with
1
[G1] as well as for 13-[G4], as indicated by H NMR. (δ
(6) Fachin, G.; Bertani, R.; Berton, A.; Gleria, M. Inorg. Chim. Acta
1988, 147, 165.
3
PhCH ) 5.4 ppm, J HH ) 12.2 Hz cis form; δ PhCH )

3802 J . Org. Chem., Vol. 61, No. 11, 1996
Launay et al.
Sch em e 4
Sch em e 5
5.8 ppm, 3J HH ) 16.6 Hz trans form; δ CHCN ) 7.1 ppm,
J H-H ) 12.2 Hz cis form; δ CHCN obscured by signals
due to aromatic protons for the trans form). 13C NMR
corroborated the presence of the two forms (see Experi-
mental Section). These observations concerning the
stereospecificity of the Wittig reaction involving den-
drimers were in agreement with that reported in the
literature for the reactions between “classical” aldehydes
and phosphorus ylides 10 or 12.6 Remarkably no differ-
ence of reactivity was detected when moving from den-
drimer of generation 1 to dendrimers of generation 2, 3,
or 4.
Rea ctivity of (S)P Cl2 Ch a in En d s. Nucleophilic
substitutions of the terminal P(S)Cl2 moieties easily
occurred when dendrimers 1-[G1]-1-[G7] were reacted
with monoallylamine (2 equiv of amine per P(S)Cl2
fragments) in the presence of triethylamine (2 equiv
per PSCl2 fragments). Dendrimers 14-[G1]-14-[G7]
arising from disubstitutions were formed in 92-95% yield
(Scheme 5). As mentioned for the preparation of the
other dendrimers these reactions can be followed rigor-
ously by 31P NMR, and the seven new dendrimers were
fully characterized. The resonance of the phosphorus
atom of the core being detected up to the sixth generation,
even one uncompleted substitution should be detected
without any doubt by 31P NMR. For the seventh genera-
tion (compound 14-[G7], 384 peripheral NH allyl groups),
even under the best conditions, structure defects cannot
be totally ruled out in the limit of NMR precision (1%).
All these macromolecules were found to be soluble in a
variety of organic solvents (THF, chloroform, dichloro-
methane ...) and perfectly stable. No difference of
reactivity was observed from generation 1 to generation
7.
eral functionalities such as hydrazones, alcohols, allyl or
propargylamines, R,â unsaturated ketones, or cinnamo-
nitrile. Thus, 33 new dendrimers were synthesized and
fully characterized. The same reactivity was observed
for generation 1 or generation 4 or generation 7. Two
exceptions have to be mentioned: due to steric effects
condensation reactions of aldehyde groups with fluo-
renone hydrazone or 4-aminobenzo-15-crown-5 appeared
to be more and more difficult to achieve when moving
from generation 1 to generation 3 or 4. Nevertheless,
dendrimers with 24 fluorenone or 48 crown ether moieties
on the surface were isolated. Investigations concerning
the chemical and physical properties of all these macro-
molecules are underway.
Exp er im en ta l Section
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
2-[G1]-2-[G4]. To a solution of 0.100 g of dendrimer 1-[G′n ]
(n ) 1, 0.070 mmol; n ) 2, 0.029 mmol; n ) 3, 0.0135 mmol;
n ) 4, 0.0065 mmol) in 10 mL of CH2Cl2 was added dropwise
under strong stirring to a suspension of hydrazine hydrate (n
) 1, 1.3 mL; n ) 2, 2.0 mL; n ) 3, 4.0 mL; n ) 4, 10.0 mL,
large excess) in 10 mL of CH2Cl2. After stirring for 2 h at room
temperature, two layers were separated. The organic layer
(lower layer) was recovered and evaporated to dryness. The
residue thus obtained was washed with ether (3 × 10 mL).
Compounds 2-[Gn ] must be used rapidly, they become in-
soluble when kept as a powder.
2-[G1]: White powder. Mp 138 °C dec. 92% yield. 31P {1H}
NMR (CDCl3) δ 52.2, 61.9; 1H NMR (CDCl3) δ 3.3 (d, J ) 10.5
Hz, 9H), 5.5 (br s, 12H), 7.2-7.6 (m, 45H). 13C{1H} NMR
(CDCl3) δ 32.9 (d, J ) 13.1 Hz), 121.4 (d, J ) 4.9 Hz), 127.1,
128.3, 132.4, 138.4 (d, J ) 14.0 Hz), 141.6, 150.5 (d, J ) 8.1
Hz), 151.0 (d, J ) 8.6 Hz). IR (KBr): 3378 (m, νNH) cm-1. Anal.
Calcd for C66H66N18O9P4S4: C, 52.59; H, 4.41; N, 16.72.
Found: C, 52.36; H, 4.28; N, 16.52.
Analogous experiments can be performed using other
unsaturated amines. For example addition of monopro-
pargylamine (6 or 48 equiv) to a THF solution of 1-[G1]
or 1-[G4] in the presence of triethylamine (6 or 48 equiv.)
led, after stirring for 12 h at room temperature, to
derivatives 15-[G1] or 15-[G4] possessing 6 or 48 terminal
NH propargyl units. Similarly treatment of 1-[G1] or
1-[G4] in THF solution with N-(trimethylsilyl)imidazole
(6 or 48 equiv) gave the dendrimers 16-[G1] or 16-[G4]
obtained quantitatively after stirring for 1 hour at room
temperature. No structure defects can be detected for
all these new dendrimers.
2-[G2]: White powder. Mp 151 °C dec. 93 % yield. 31P {1H}
NMR (CDCl3) δ 52.6, 62.2 (br s). 1H NMR (CDCl3) δ 3.3 (d, J
) 10.4 Hz, 27H), 5.5 (br s, 24H), 7.2-7.6 (m, 105H). 13C{1H}
NMR (CDCl3) δ 32.9 (d, J ) 11.9 Hz), 121.4 (d, J ) 4.3 Hz),
121.4 (br s), 127.1, 128.1, 128.3, 132.0, 132.4, 138.5 (d, J )
14.7 Hz), 141.6, 150.5 (d, J ) 7.1 Hz), 151.1 (m). IR (KBr):
3391 (m, νNH) cm-1. Anal. Calcd for C156H156N42O21P10S10: C,
52.26; H, 4.38; N, 16.40. Found: C, 51.86; H, 4.25; N, 16.22.
2-[G3]: White powder. Mp 164 °C dec. 91 % yield. 31P {1H}
NMR (CDCl3) δ 52.7, 62.1, 62.2. 1H NMR (CDCl3) δ 3.3 (d, J
) 10.0 Hz, 63 H), 5.5 (br s, 48 H), 7.1-7.6 (m, 225 H). 13C{1H}
NMR (CDCl3) δ 32.9 (d, J ) 10.4 Hz), 121.4 (br s), 127.1, 128.1
(br s), 132.0, 132.3, 138.6 (m), 141.6, 150.4 (d, J ) 6.8 Hz),
151.1 (m). IR (KBr): 3392 (m, νNH) cm-1
. Anal. Calcd for
Con clu sion
C336H336N90O45P22S22: C, 52.13; H, 4.37; N, 16.28. Found: C,
51.86; H, 4.19; N, 16.09.
It was demonstrated that classical organic chemistry
can be developed on the surface of phosphorus-containing
dendrimers whatever the size of these macromolecules,
i.e. whatever the number of generation. Dense packing
effects did not prevent the preparation of a variety of
multi-difunctionalized species possessing various periph-
2-[G4]: White powder. Mp 170 °C dec. 90 % yield. 31P {1H}
NMR (CDCl3) δ 52.7, 62.1, 62.2. 1H NMR (CDCl3) δ 3.3 (d, J
) 10.2 Hz, 135 H), 5.5 (br s, 96 H), 7.1-7.6 (m, 465 H). IR
(KBr): 3390 (m,
ν
NH) cm-1
.
Anal. Calcd for C696H696-
N186O93P46S46: C, 52.07; H, 4.37; N, 16.22. Found: C, 51.91;
H, 4.27; N, 16.10.

Phosphorus-Containing Dendrimers
J . Org. Chem., Vol. 61, No. 11, 1996 3803
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
3-[G1], 3-[G4]. To a solution of 0.300 g of dendrimer 1-[G′n ]
(n ) 1, 0.211 mmol; n ) 4, 0.0195 mmol) in 10 mL of
chloroform was added dropwise a solution of methylhydrazine
(n ) 1, 135 µL, 2.53 mmol; n ) 4, 100 µL, 1.87 mmol, 100%
excess) in 10 mL of chloroform, at room temperature. The
mixture was stirred for 2 h and then evaporated to dryness.
The powder thus obtained was washed with ether (10 mL).
3-[G1]: White powder. Mp 153 °C dec. 31P {1H} NMR
(CDCl3) δ 52.4, 62.4. 1H NMR (CDCl3) δ 2.9 (s, 18 H), 3.3 (d,
J ) 10.4 Hz, 9 H), 5.5 (br s, 6 H), 7.0 (dd, J ) 8.5 Hz, J ) 1.4
Hz, 12 H), 7.3 (dd, J ) 8.5 Hz, J ) 1.1 Hz, 6 H), 7.4 (s, 6 H),
7.5 (d, J ) 8.5 Hz, 12 H), 7.6 (s, 3 H), 7.7 (d, J ) 8.5 Hz, 6 H).
13C {1H} NMR (CDCl3) δ 32.4 (d, J ) 12.8 Hz), 34.0, 120.9 (d,
J ) 4.2 Hz), 126.0, 127.8, 132.0, 133.0, 133.8, 137.6 (d, J )
13.8 Hz), 149.5 (d, J ) 7.6 Hz), 150.5 (d, J ) 8.5 Hz). IR (KBr)
3376 (m, νNH) cm-1. MS m/z 1591 [M + 1]+. Anal. Calcd for
C72H78N18O9P4S4: C, 54.33; H, 4.93; N, 15.84. Found: C, 54.07;
H, 4.81; N, 15.71.
) 9.3 Hz, 135 H), 3.6 (m, 96 H), 7.0-7.6 (m, 465 H). 13C {1H}
NMR (CDCl3) δ 32.3 (d, J ) 13.0 Hz), 50.1, 51.5, 57.3, 58.5,
120.8 (d, J ) 3.6 Hz), 120.8 (m), 126.5, 127.6 (br s), 131.5,
131.8, 134.1, 138.0-139.0 (m), 149.7 (d, J ) 7.3 Hz), 150.5 (d,
J ) 6.6 Hz), 150.9 (d, J ) 6.4 Hz). IR (KBr): 3400 (br; νOH
cm-1
Anal. Calcd for C984H1224N234O141P46S46: C, 55.01; H,
5.74; N, 15.25. Found: C, 54.73; H, 5.70; N, 15.16.
)
.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
7-[G1], 7-[G3]. A solution of 0.300 g of dendrimer 1-[G′n ] (n
) 1, 0.211 mmol; n ) 3, 0.0405 mmol) and 9-fluorenone
hydrazone 6 (n ) 1, 0.492 g, 2.532 mmol; n ) 3, 0.378 g, 1.944
mmol) in 20 mL of chloroform was stirred at room temperature
(n ) 1, 1 week; n ) 3, 3 weeks) in the presence of molecular
sieve (4 Å). Molecular sieve was eliminated by centrifugation
and then the solution was evaporated to dryness. The result-
ing powder was washed with 2 × 10 mL of a chloroform/ether
(1/1) mixture to eliminate excess of 6.
7-[G1]: Orange yellow powder. Mp 155 °C dec. 70% yield.
31P {1H} NMR (CDCl3) δ 52.6, 61.6. 1H NMR (CDCl3) δ 3.4
(d, J ) 10.3 Hz, 9 H). 7.4-8.4 (m, 87 H), 8.5 (s, 6 H). 13C
{1H} NMR (CDCl3) δ 32.5 (d, J ) 13.1 Hz), 119.1, 121.0 (d, J
) 3.2 Hz), 121.4 (d, J ) 4.8 Hz), 122.2, 127.4, 127.5, 127.9,
129.5, 130.0, 130.5, 130.8, 130.9, 131.1, 131.9, 136.1, 138.3 (d,
J ) 13.5 Hz), 140.9, 141.7, 150.6 (d, J ) 7.3 Hz), 152.1 (d, J )
7.3 Hz), 158.0, 160.0, 160.1. UV (CH2Cl2): 372 (ꢀ ) 5.1 × 104),
354 (ꢀ ) 8.7 × 104), 338 (ꢀ ) 9.4 × 104), 304 (ꢀ ) 8.5 × 104),
296 (ꢀ ) 9.9 × 104), 284 (ꢀ ) 11.6 × 104), 268 (ꢀ ) 17.4 × 104),
266 (ꢀ ) 17.9 × 104), 260 (ꢀ ) 17.3 × 104) nm. MS: m/z 2479
[M + 1]+. Anal. Calcd for C144H102N18O9P4S4: C, 69.72; H,
4.14; N, 10.16. Found: C, 69.69; H, 4.11; N, 10.07.
3-[G4]: White powder. Mp: 150 °C dec. 85% yield. 31P {1H}
NMR (CDCl3) δ 52.4, 62.4, 62.5 (br s). 1H NMR (CDCl3) δ 2.8
(s, 144 H), 3.4 (m, 135 H), 5.5 (br s, 48 H), 7.0-7.8 (m, 465 H).
13C {1H} NMR (CDCl3) δ 32.3 (m), 34.0, 121.2 (d, J ) 4.3 Hz),
127.6, 130.8, 131.1, 131.5, 132.9, 133.8, 139.0, 150.3 (m), 150.8
(d, J ) 6.2 Hz), 154.4 (d, J ) 7.4 Hz). IR (KBr) 3412 (m, νNH
)
cm-1. Anal. Calcd for C744H792N186O93P46S46: C, 53.42; H, 4.77;
N, 15.57. Found: C, 53.09; H, 4.63; N, 15.41.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
5-[G1]-5-[G4]. A solution of 0.300 g of dendrimer 1-[G′n ] (n
) 1, 0.211 mmol; n ) 2, 0.0877 mmol; n ) 3, 0.0405 mmol; n
) 4, 0.0195 mmol) and 1-amino-4-(2-hydroxyethyl)piperazine
(4) (n ) 1, 0.368 g, 2.532 mmol; n ) 2, 0.306 g, 2.105 mmol; n
) 3, 0.282 g, 1.944 mmol; n ) 4, 0.272 g, 1.872 mmol, 100%
excess) in 20 mL of chloroform was refluxed for 48 h in the
presence of molecular sieve (4 Å). Molecular sieve was
eliminated by centrifugation, and then the solution was
evaporated to dryness. The resulting powder was washed with
2 × 10 mL of a chloroform/ether (1/10) mixture to eliminate
excess of 4.
7-[G3]: Orange yellow powder. Mp 135 °C dec. 40% yield.
31P {1H} NMR (CDCl3) δ 52.6, 61.6, 62.4, 62.6. 1H NMR
(CDCl3) δ 3.3 (m, 63 H), 7.2-8.3 (m, 393 H), 8.4 (s, 24 H). 13C
{1H} NMR (CDCl3) δ 32.4 (d, J ) 12.6 Hz), 119.2, 121.0-121.4
(m), 122.2, 127.2, 127.5, 127.7 (br s), 129.4, 130.0, 130.5, 130.8
(br s), 131.0, 131.3-131.5 (m), 136.0, 138.5 (m), 140.8, 141.7,
150.5 (d, J ) 7.3 Hz), 150.7 (d, J ) 6.6 Hz), 152.1 (d, J ) 7.1
Hz), 158.1, 159.9 (br s). Anal. Calcd for C648H480
-
N90O45P22S22: C, 66.90; H, 4.16; N, 10.84. Found: C, 66.71;
H, 4.01; N, 10.75.
5-[G1]: White powder. Mp 67 °C dec. 78% yield. 31P {1H}
NMR (CDCl3) δ 52.4, 62.4. 1H NMR (CDCl3) δ 2.5-2.6 (m, 36
H), 2.85 (m, 6 H), 3.1 (m, 24 H), 3.3 (d, J ) 10.4 Hz, 9 H), 3.6
(m, 12 H), 7.1 (d, J ) 8.0 Hz, 12 H), 7.3 (d, J ) 8.4 Hz, 6 H),
7.45 (s, 6 H), 7.5 (d, J ) 8.0 Hz, 12 H), 7.6 (s, 3H), 7.7 (d, J )
8.4 Hz, 6 H). 13C {1H} NMR (CDCl3) δ 32.4 (d, J ) 13.0 Hz),
50.4, 51.5, 57.3, 58.5, 120.9 (d, J ) 4.3 Hz), 126.5, 127.7, 132.0,
132.9, 134.1, 137.6 (d, J ) 14.9 Hz), 149.7 (d, J ) 7.3 Hz),
150.5 (d, J ) 7.3 Hz). IR (KBr) 3400 (br, νOH) cm-1. MS m/z
2185 [M + 1]+. Anal. Calcd for C102H132N24O15P4S4: C, 56.03;
H, 6.08; N, 15.37. Found: C, 55.81; H, 7.95; N, 15.03.
5-[G2]: Pale yellow powder. Mp 72 °C dec. 95% yield. 31P
{1H} NMR (CDCl3) δ 52.6, 62.4, 62.6. 1H NMR (CDCl3) δ 2.5-
2.6 (m, 72 H), 2.85 (m, 12 H), 3.1 (br s, 48 H), 3.3 (d, J ) 10.4
Hz, 18 H), 3.35 (d, J ) 10.4 Hz, 9 H), 3.6 (m, 24 H), 7.1 (d, J
) 8.0 Hz, 24 H), 7.2-7.3 (m, 18 H), 7.4 (s, 12 H), 7.5 (d, J )
8.0 Hz, 24 H), 7.6 (s, 9 H), 7.65 (d, J ) 8.6 Hz, 12 H), 7.7 (d,
J ) 8.6 Hz, 6 H) ppm. 13C {1H} NMR (CDCl3) δ 32.4 (d, J )
13.0 Hz), 50.4, 51.5, 57.3, 58.5, 120.9 (d, J ) 4.5 Hz), 121.1 (d,
J ) 4.3 Hz), 126.5, 127.6, 127.8, 131.6, 132.0, 132.9, 134.1,
138.0 (d, J ) 13.1 Hz), 149.7 (d, J ) 7.5 Hz), 150.3 (d, J ) 7.3
Hz), 150.6 (d, J ) 7.4 Hz). IR (KBr) 3400 (br, νOH) cm-1. Anal.
Calcd for C228H288N54O33P10S10: C, 55.40; H, 5.87; N, 15.30.
Found: C, 55.28; H, 5.78; N, 15.11.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
9-[G1], 9-[G2], 9-[G4]. A solution of 0.300 g of dendrimer
1-[G′n ] (n ) 1, 0.211 mmol; n ) 2, 0.0877 mmol; n ) 4, 0.0195
mmol) and 4′-aminobenzo-15-crown-5 8 (n ) 1, 0.717 g, 2.532
mmol; n ) 2, 0.596 g, 2.105 mmol; n ) 4, 0.531 g, 1.872 mmol;
100% excess) in 20 mL of THF was refluxed (n ) 1, 1 week; n
) 2, 2 weeks, n ) 4, 3 weeks) in the presence of molecular
sieve (4 Å). After centrifugation, the solution was evaporated
to dryness. The resulting powder was washed with 3 × 15
mL of a THF/ether (1/10) mixture to eliminate excess of 8.
9-[G1]: Yellow powder. Mp 70 °C dec. 70% yield. 31P {1H}
NMR (CDCl3) δ 52.5, 61.6. 1H NMR (CDCl3) δ 3.3 (d, J ) 10.6
Hz, 9 H), 4.0 (m, 96 H), 6.8 (m, 18 H), 7.3 (d, J ) 8.6 Hz, 18
H), 7.6 (s, 3 H), 7.7 (d, J ) 8.6 Hz, 6 H), 7.9 (d, J ) 8.4 Hz, 12
H), 8.4 (s, 6 H) ppm. 13C {1H} NMR (CDCl3) δ 32.4 (d, J )
13.0 Hz), 68.2-70.4 (m), 107.1, 112.2, 113.8, 120.9 (d, J ) 4.4
Hz), 121.1 (d, J ) 4.7 Hz), 127.8, 129.3, 131.9, 133.0, 138.1 (d,
J ) 13.5 Hz), 144.8, 147.2, 148.9, 150.5 (d, J ) 7.9 Hz), 152.0
(d, J ) 7.6 Hz), 156.5. MS: m/z 3013 [M + 1]+. Anal. Calcd
for C150H168N12O39P4S4: C, 59.73; H, 5.62; N, 5.58. Found: C,
59.51; H, 5.57; N, 5.41.
9-[G2]: Pale yellow powder. Mp 106 °C dec. 60% yield. 31P
{1H} NMR (CDCl3) δ 52.6, 61.8, 65.4. 1H NMR (CDCl3) δ 3.3
(d, J ) 10.5 Hz, 27 H), 3.7-4.2 (m, 192 H), 6.7-6.9 (m, 36 H),
7.2-7.8 (m, 93 H), 8.4 (s, 12 H). 13C {1H} NMR (CDCl3) δ 32.3
(d, J ) 13.0 Hz), 32.4 (d, J ) 13.1 Hz), 68.1-70.4 (m), 107.1,
112.2, 113.7, 120.8 (d, J ) 4.4 Hz), 121.1 (d, J ) 4.3 Hz), 127.6,
127.8, 129.3, 131.2, 132.0, 133.0, 138.0-140.0 (m), 144.8, 147.1,
148.8, 150.5 (d, J ) 7.3 Hz), 150.9 (d, J ) 8.7 Hz), 151.9 (d, J
) 7.4 Hz), 156.2. Anal. Calcd for C324H360N30O81P10S10: C,
58.95; H, 5.50; N, 6.37. Found: C, 58.61; H, 5.37; N, 6.21.
9-[G4]: Yellow powder. Mp 116 °C dec. 50% yield. 31P {1H}
NMR (CDCl3) δ 52.6, 61.8, 62.1, 62.4, 62.6. 1H NMR (CDCl3)
δ 3.2-3.3 (m, 135 H), 3.7-4.2 (m, 768 H), 6.7-6.9 (m, 144 H),
7.2-7.8 (m, 417 H), 8.3 (br s, 48 H). 13C {1H} NMR (CDCl3) δ
32.3 (m), 68.2-70.3 (m), 107.1, 112.2, 113.8, 121.1 (d, J ) 3.6
5-[G3]: Pale yellow powder. Mp 53 °C dec. 85% yield. 31P
{1H} NMR (CDCl3) δ 52.4, 62.3, 62.5 (br s). 1H NMR (CDCl3)
δ 2.5-2.6 (m, 144 H), 3.0 (m, 24 H), 3.1 (m, 96 H), 3.4 (d, J )
7.0 Hz, 63 H), 3.6 (m, 48 H), 7.0-7.6 (m, 225 H). 13C {1H}
NMR (CDCl3) δ 32.3 (d, J ) 12.6 Hz), 50.2, 51.6, 57.3, 58.5,
120.8 (d, J ) 3.6 Hz), 121.1 (m), 126.5, 127.5 (br s), 131.4,
131.8, 134.0, 138.0-139.0 (m), 149.7 (d, J ) 7.3 Hz), 150.5 (d,
J ) 7.3 Hz), 150.6 (d, J ) 6.9 Hz). IR (KBr) 3400 (br, νOH
)
cm-1. Anal. Calcd for C480H600N114O69P22S22: C, 55.13; H, 5.78;
N, 15.27. Found: C, 55.01; H, 5.59; N, 15.03.
5-[G4]: Pale yellow powder. Mp 83 °C dec. 51% yield. 31P
{1H} NMR (CDCl3) δ 52.4, 62.4, 62.5 (br s). 1H NMR (CDCl3)
δ 2.5-2.6 (m, 288 H), 2.8 (m, 48 H), 3.1 (m, 192 H), 3.2 (d, J

3804 J . Org. Chem., Vol. 61, No. 11, 1996
Launay et al.
Hz), 127.6, 129.3, 131.4 (m), 133.0, 138.0-140.0 (m), 144.8,
Hz), 121.2 (d, J ) 5.8 Hz), 121.5 (d, J ) 4.7 Hz), 127.8, 128.2,
130.0, 130.2, 131.8, 132.0, 138.4 (d, J ) 10.8 Hz), 146.8, 148.6,
150.6 (d, J ) 7.4 Hz), 151.5 (d, J ) 7.3 Hz), 151.9 (d, J ) 7.4
Hz). IR (KBr): 2216 (s; νCtN) cm-1. MS: m/z 1561 [M + 1]+.
Anal. Calcd for C78H60N12O9P4S4: C, 60.00; H, 3.87; N, 10.76.
Found: C, 59.64; H, 3.73; N, 10.59.
147.1, 148.8, 150.0-156.0 (m), 156.5. Anal. Calcd for C1368
-
H1512N138O333P46S46: C, 58.44; H, 5.42; N, 6.87. Found: C,
58.33; H, 5.38; N, 6.74.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
11-[G1]-11-[G4]. A solution of 0.300 g of dendrimer 1-[G′n ]
(n ) 1, 0.211 mmol; n ) 2, 0.0877 mmol; n ) 3, 0.0405 mmol;
n ) 4, 0.0195 mmol) and (acetylmethylene)triphenylphos-
phorane (10) (n ) 1, 0.403 g, 1.266 mmol; n ) 2, 0.335 g, 1.052
mmol; n ) 3, 0.309 g, 0.972 mmol; n ) 4, 0.298 g, 0.936 mmol)
in 20 mL of THF was refluxed for 48 h. The solution was then
evaporated to dryness. The resulting past was washed with
3 × 20 mL of a THF/pentane/ether (1/10/10) mixture to
eliminate triphenylphosphine oxide. Dendrimers 11-[Gn ] were
obtained as powders.
13-[G4]: Pale yellow powder. Mp 133 °C dec. 62% yield.
31P {1H} NMR (CDCl3) δ 52.6, 61.4 62.3 (br s), 62.8, 63.0. 1H
NMR (CDCl3) δ 3.3 (d, J ) 10.0 Hz, 135 H), 5.3 (d, J ) 12.1
Hz, (48 × 0.2) H), 5.7 (d, J ) 16.3 Hz, (48 × 0.8) H), 7.0 (d, J
) 12.1 Hz, (48 × 0.2) H), 7.2-7.7 (m, (417 + 48 × 0.8) H). 13C
{1H} NMR (CDCl3) δ 32.3 (d, J ) 13.6 Hz), 94.3, 95.7, 116.6,
117.4, 120.9 (d, J ) 3.9 Hz), 121.2 (d, J ) 9.2 Hz), 121.3 (d, J
) 8.7 Hz), 127.5 (br s), 127.8, 128.2, 129.9, 130.1, 131.3, 131.5,
132.0, 138.7 (m), 146.7, 148.5, 150.6 (d, J ) 7.4 Hz), 150.5-
150.8 (m), 151.4 (d, J ) 7.3 Hz), 151.8 (d, J ) 7.7 Hz). IR
11-[G1]: Pale yellow powder. Mp 59 °C dec. 59% yield. 31P
{1H} NMR (CDCl3) δ 52.6, 61.6. 1H NMR (CDCl3) δ 2.3 (s, 18
H), 3.4 (d, J ) 10.6 Hz, 9 H), 6.6 (d, J ) 16.3 Hz, 6 H), 7.2 (dd,
J ) 6.7 Hz, J ) 1.4 Hz, 12 H), 7.3 (dd, J ) 8.6 Hz, J ) 1.2 Hz,
6 H), 7.4 (d, J ) 16.3 Hz, 6 H), 7.5 (d, J ) 6.7 Hz, 12 H), 7.6
(s, 3 H), 7.7 (d, J ) 8.6 Hz, 6 H). 13C {1H} NMR (CDCl3) δ
26.9, 32.4 (d, J ) 13.1 Hz), 120.9 (d, J ) 4.2 Hz), 121.3 (d, J
) 4.7 Hz), 126.5, 127.8, 128.9, 131.1, 131.9, 138.2 (d, J ) 14.3
Hz), 141.5, 150.5 (d, J ) 8.0 Hz), 154.4 (d, J ) 7.2 Hz), 197.5.
IR (KBr) 1689 (s, νCdO(s-cis)), 1666 (s, νCdO(s-trans)) cm-1 IR (THF)
(KBr):
2216 (s, νCtN
)
cm-1
.
Anal.
Calcd for
C792H648N138O93P46S46: C, 57.70; H, 3.96; N, 11.72. Found: C,
54.47; H, 3.81; N, 11.51.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
14-[G1]-14-[G7]. To a solution of 0.100 g of dendrimer 1-[Gn ]
(n ) 1, 0.110 mmol; n ) 2, 0.0418 mmol; n ) 3, 0.0186 mmol;
n ) 4, 0.0088 mmol; n ) 5, 0.0043 mmol; n ) 6, 0.00214 mmol;
n ) 7, 0.00106 mmol) in 10 mL of THF was added triethyl-
amine (n ) 1, 101 µL, 0.726 mmol; n ) 2, 77 µL, 0.552 mmol;
n ) 3, 68 µL, 0.491 mmol; n ) 4, 65 µL, 0.465 mmol; n ) 5, 63
µL, 0.454 mmol; n ) 6, 63 µL, 0.452 mmol; n ) 7, 62 µL, 0.448
mmol; 10% excess) then allylamine (n ) 1, 55 µL, 0.726 mmol;
n ) 2, 41 µL, 0.552 mmol; n ) 3, 37 µL, 0.491 mmol; n ) 4, 35
µL, 0.465 mmol; n ) 5, 34 µL, 0.454 mmol; n ) 6, 34 µL, 0.452
mmol; n ) 7, 34 µL, 0.448 mmol; 10% excess). The resulting
mixture was stirred for 12 h at room temperature and then
filtered. The solution was evaporated to dryness to give an
oil (14-[G1]) or a powder, which was washed with 2 × 10 mL
of a pentane/ether (1/1) mixture.
1695 (s, νCdO(s-cis)), 1672 (s, νCdO(s-trans)) cm-1
. MS: m/z 1663
[M + 1]+. Anal. Calcd for C84H78N6O15P4S4: C, 60.64; H, 4.73;
N, 5.05. Found: C, 60.57; H, 4.63; N, 4.95.
11-[G2]: Yellow powder. Mp: 56 °C dec. 60% yield. 31P
{1H} NMR (CDCl3) δ 52.8, 61.7, 62.4. 1H NMR (CDCl3) δ 2.3
(s, 36 H), 3.3 (d, J ) 10.5 Hz, 18 H), 3.4 (d, J ) 9.3 Hz, 9 H),
6.6 (d, J ) 16.2 Hz, 12 H), 7.1-7.3 (m, 42 H), 7.3 (d, J ) 16.2
Hz, 12 H), 7.5 (d, J ) 7.9 Hz, 24 H), 7.6 (s, 9 H), 7.65 (d, J )
8.6 Hz, 12 H), 7.75 (d, J ) 8.7 Hz, 6 H). 13C {1H} NMR (CDCl3)
δ 27.0, 32.4 (d, J ) 13.0 Hz), 120.8 (d, J ) 3.4 Hz), 121.3 (d,
J ) 4.7 Hz), 126.4, 127.6, 127.8, 128.9, 131.1, 131.4, 131.5,
138.5 (d, J ) 13.9 Hz), 141.4, 150.5 (d, J ) 5.8 Hz), 150.7 (d,
J ) 7.1 Hz), 151.4 (d, J ) 7.3 Hz), 197.5. IR (KBr) 1689 (s,
14-[G1]: Yellow oil: 92% yield. 31P {1H} NMR (CDCl3) δ
52.2, 68.6. 1H NMR (CDCl3) δ 3.1 (d, J ) 9.5 Hz, 9 H), 3.3 (m,
6 H), 3.6 (m, 12H), 5.1 (m, 12H), 5.8 (m, 6H), 7.1 (dd, J ) 8.6
Hz, J ) 1.5 Hz, 6H), 7.4 (s, 3H), 7.7 (d, J ) 8.6 Hz, 6 H). 13C
{1H} NMR (CDCl3) δ 30.9 (d, J ) 11.2 Hz), 43.7, 115.4, 121.2
(d, J ) 4.5 Hz), 127.5, 133.1, 135.7 (d, J ) 12.2 Hz), 136.0 (d,
ν
CdO(s-cis)), 1666 (s, νCdO(s-trans)
)
cm-1
.
Anal. Calcd for
C192H180N18O33P10S10: C, 59.16; H, 4.65; N, 6.47. Found: C,
58.95; H, 4.51; N, 6.35.
11-[G3]: Pale yellow powder. Mp 63 °C dec. 72% yield. 31P
{1H} NMR (CDCl3) δ 52.6, 61.7, 62.4, 62.7. 1H NMR (CDCl3)
δ 2.3 (s, 72 H), 3.3 (d, J ) 10.5 Hz, 63 H), 6.6 (d, J ) 16.0 Hz,
24 H), 7.2-7.8 (m, 225 H). 13C {1H} NMR (CDCl3) δ 26.9, 32.3
(d, J ) 12.9 Hz), 121.3 (d, J ) 4.8 Hz), 126.5, 127.7, 127.6,
128.9, 131.1, 131.3, 131.5, 132.0, 138.0-138.6 (m), 141.4,
150.5-151.8 (m), 151.4 (d, J ) 7.3 Hz), 197.5. IR (KBr) 1689
J ) 7.9 Hz), 150.3 (d, J ) 8.3 Hz). IR (THF): 3376 (m, νNH
)
-
cm-1 MS: m/z 1033.2 [M]+. Anal. Calcd for C42H60
.
N12O3P4S4: C, 48.83; H, 5.85; N, 16.27. Found: C, 48.49; H,
5.68; N, 16.12.
14-[G2]: White powder. Mp 98 °C dec. 95% yield. 31P {1H}
NMR (CDCl3) δ 51.8, 61.8, 68.7. 1H NMR (CDCl3) δ 3.0 (d, J
) 7.3 Hz, 18 H), 3.1 (d, J ) 9.3 Hz, 9 H), 3.3 (m, 12H), 3.5 (m,
24 H), 5.1 (m, 24 H), 5.8 (m, 12 H), 7.1-7.7 (m, 45 H). 13C
{1H} NMR (CDCl3) δ 30.8 (d, J ) 11.2 Hz), 33.0 (d, J ) 12.8
Hz), 43.7, 115.4, 121.5 (m), 127.4, 128.3, 132.5, 132.7, 136.0
(m), 138.5 (d, J ) 12.1 Hz), 150.5 (d, J ) 7.2 Hz), 150.9 (d, J
(s, νCdO(s-cis)), 1666 (s, νCdO(s-trans)) cm-1
. Anal. Calcd for
C408H384N42O69P22S22: C, 58.57; H, 4.63; N, 7.03. Found: C,
58.41; H, 4.53; N, 6.89.
11-[G4]: Pale yellow powder. Mp 148 °C dec. 65% yield.
31P {1H} NMR (CDCl3) δ 52.5, 61.6, 62.3, 62.7, 63.0. 1H NMR
(CDCl3) δ 2.3 (s, 144 H), 3.3 (d, J ) 10.2 Hz, 135 H), 6.5 (d, J
) 16.1 Hz, 48 H), 7.2-7.8 (m, 465 H). 13C {1H} NMR (CDCl3)
δ 26.9, 32.3 (d, J ) 13.2 Hz), 121.3 (d, J ) 4.9 Hz), 126.5, 127.6,
127.8 (br s), 128.9, 131.1, 131.3, 131.5, 138.5-139.0 (m), 141.4,
150.5-151.8 (m), 151.4 (d, J ) 8.1 Hz), 197.5. IR (KBr) 1689
) 8.2 Hz). IR (KBr): 3367 (m, νNH) cm-1
. Anal. Calcd for
C108H144N30O9P10S10: C, 49.19; H, 5.50; N, 15.94. Found: C,
48.91; H, 5.41; N, 15.79.
14-[G3]: White powder. Mp 109 °C dec. 95% yield. 31P
{1H} NMR (CDCl3) δ 51.8, 61.7, 68.7. 1H NMR (CDCl3) δ 3.1
(d, J ) 9.5 Hz, 36H), 3.2 (d, J ) 9.3 Hz, 27H), 3.3 (m, 24H),
3.5 (m, 48H), 5.1 (m, 48H), 5.8 (m, 24H), 7.1-7.7 (m, 105H).
13C {1H} NMR (CDCl3) δ 30.8 (d, J ) 10.9 Hz), 32.9 (d, J )
12.7 Hz), 43.7, 115.4, 121.5 (m), 127.4, 128.2, 128.4, 132.0,
132.7, 136.0 (m), 138.7 (d, J ) 12.4 Hz), 150.5 (d, J ) 7.2 Hz),
(s, νCdO(s-cis)), 1666 (s, νCdO(s-trans)) cm-1
. Anal. Calcd for
C840H792N90O141P46S46: C, 58.31; H, 4.61; N, 7.28. Found: C,
58.12; H, 4.47; N, 7.21.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
13-[G1], 13-[G4]. A solution of 0.300 g of dendrimer 1-[G′n ]
(n ) 1, 0.211 mmol, n ) 4, 0.0195 mmol) and (cyanomethyl-
ene)triphenylphosphorane (12) (n ) 1, 0.381 g, 1.266 mmol; n
) 4, 0.282 g, 0.936 mmol) in 20 mL of THF was refluxed for
12 h. The solution was then evaporated to dryness. The
resulting paste was washed with 3 × 15 mL of a THF/pentane
(1/1) mixture to eliminate triphenylphosphine oxide. Den-
drimers 11-[Gn ] were obtained as powders.
13-[G1]: Pale yellow powder. Mp 128 °C dec. 58% yield.
31P {1H} NMR (CDCl3) δ 52.7, 61.5. 1H NMR (CDCl3) δ 3.4
(d, J ) 10.6 Hz, 9 H), 5.4 (d, J ) 12.2 Hz, (6 × 0.2) H), 5.8 (d,
J ) 16.6 Hz, (6 × 0.8) H), 7.1 (d, J ) 12.2 Hz, (6 × 0.2) H),
7.2-7.8 (m, (39 + 6 × 0.8) H). 13C {1H} NMR (CDCl3) δ 32.4
(d, J ) 13.2 Hz), 94.4, 95.8, 116.6, 117.3, 120.9 (d, J ) 3.9
150.9 (m). IR (KBr): 3367 (m, νNH) cm-1
. Anal. Calcd for
C240H312N66O21P22S22: C, 49.32; H, 5.38; N, 15.82. Found: C,
49.11; H, 5.24; N, 15.61.
14-[G4]: White powder: Mp 112 °C dec. 94% yield. 31P
{1H} NMR (CDCl3) δ 51.5, 61.3, 61.7, 68.7. 1H NMR (CDCl3)
δ 3.1 (d, J ) 9.4 Hz, 72H), 3.2 (m, 63H), 3.3 (m, 48H), 3.5 (m,
96H), 5.1 (m, 96H), 5.8 (m, 48H), 7.1-7.7 (m, 225H). 13C {1H}
NMR (CDCl3) δ 30.8 (d, J ) 11.3 Hz), 32.9 (d, J ) 12.7 Hz),
43.7, 115.4, 121.5 (m), 127.4, 128.2, 132.0, 132.6, 136.0 (m),
138.7 (m), 150.5 (d, J ) 7.0 Hz), 151.1 (d, J ) 6.9 Hz). IR
(KBr): 3369 (m,
ν
NH) cm-1
.
Anal. Calcd for C504H648-
N138O45P46S46: C, 49.38; H, 5.33; N, 15.77. Found: C, 49.06;
H, 5.21; N, 15.67.

Phosphorus-Containing Dendrimers
J . Org. Chem., Vol. 61, No. 11, 1996 3805
14-[G5]: White powder: Mp 111 °C dec. 31P {1H} NMR
(CDCl3) δ 51.8, 61.8 (br s), 68.6. 1H NMR (CDCl3) δ 3.1 (d, J
) 9.1 Hz, 144H), 3.2 (m, 135H), 3.3 (m, 96H), 3.5 (m, 192H),
5.1 (m, 192H), 5.8 (m, 96H), 7.1-7.7 (m, 465H). 13C {1H} NMR
(CDCl3) δ 30.8 (d, J ) 11.3 Hz), 32.9 (d, J ) 12.8 Hz), 43.7,
115.5, 121.6 (m), 127.4, 128.2, 132.0, 132.7, 136.0 (m), 138.7
(d, J ) 13.0 Hz), 150.6 (d, J ) 7.4 Hz), 151.1 (d, J ) 6.8 Hz).
) 13.0 Hz, J ) 6.6, Hz, J ) 2.5 Hz, 6 H), 3.85 (dddd, J ) 17.7
Hz, J ) 13.0 Hz, J ) 6.7 Hz, J ) 2.5 Hz, 6 H), 7.26 (dd, J )
8.6 Hz, J ) 1.3 Hz, 6 H), 7.53 (br s, 3 H), 7.63 (d, J ) 8.6 Hz,
6 H). 13C {1H} NMR (CDCl3) δ 30.3, 30.4 (d, J ) 12.0 Hz),
70.8, 80.6 (d, J ) 8.2 Hz), 120.8 (d, J ) 4.9 Hz), 127.3, 132.4,
136.0 (d, J ) 12.5 Hz), 150.0 (d, J ) 8.2 Hz). IR (KBr): 3330
(br, νNsH), 3290 (m, νtCsH) cm-1. MS: m/z 1021 [M + 1]+. Anal.
Calcd for C42H48N12O3P4S4: C, 49.40; H, 4.74; N, 16.46.
Found: C, 49.18; H, 4.61; N, 16.40.
IR (KBr): 3366 (m, νNH) cm-1
. Anal. Calcd for C1032H1320-
N282O93P94S94: C, 49.41; H, 5.30; N, 15.74. Found: C, 49.18;
H, 5.16; N, 15.52.
15-[G4]: Pale yellow powder. Mp 60 °C dec. 58% yield. 31P
{1H} NMR (CDCl3) δ 52.6, 62.5 (br s), 67.5. 1H NMR (CDCl3)
2.2 (br s, 48 H), 3.1 (d, J ) 9.1 Hz, 72 H), 3.3 (d, J ) 8.2 Hz,
63 H), 3.4 (m, 48 H), 3.7-3.8 (m, 96 H), 7.1-7.6 (m, 225 H).
13C {1H} NMR (CDCl3) δ 30.3, 30.5 (d, J ) 10.8 Hz), 30.9 (d,
J ) 9.8 Hz), 31.9 (d, J ) 13.0 Hz), 70.8, 80.7 (d, J ) 8.0 Hz),
121.0 (d, J ) 3.6 Hz), 127.1, 127.7, 131.6, 132.0, 136.2 (d, J )
12.5 Hz), 138.0-139.0 (m), 150.3 (d, J ) 7.7 Hz), 150.7 (d, J )
14-[G6]: White powder: Mp 117 °C dec. 95% yield. 31P
{1H} NMR (CDCl3) δ 51.8, 61.8 (br s), 68.5. 1H NMR (CDCl3)
δ 3.1 (d, J ) 9.1 Hz, 288H), 3.2 (m, 279H), 3.3 (m, 192H), 3.5
(m, 384H), 5.1 (m, 384H), 5.7-5.9 (m, 192H), 7.1-7.7 (m,
945H). 13C {1H} NMR (CDCl3) δ 30.8 (d, J ) 11.3 Hz), 32.9
(d, J ) 12.8 Hz), 43.7, 115.3, 121.5 (br s), 127.4, 128.1, 128.2,
132.0, 132.7, 135.9 (d, J ) 14.5 Hz), 136.0 (d, J ) 7.2 Hz),
138.7 (m), 150.5 (d, J ) 7.3 Hz), 151.2 (d, J ) 6.9 Hz). IR
8.3 Hz). IR (KBr): 3401 (br, νNsH), 3292 (m, νtCsH) cm-1
.
(KBr): 3369 (m, νNH) cm-1
. Anal. Calcd for C2088H2664-
Anal. Calcd for C504H552N138O45P46S46: C, 49.77; H, 4.57; N,
15.89. Found: C, 49.51; H, 4.45; N, 15.71.
N570O189P190S190: C, 49.42; H, 5.29; N, 15.73. Found: C, 49.21;
H, 5.17; N, 15.39.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
16-[G1], 16-[G4]. To a solution of 0.300 g of dendrimer 1-[Gn ]
(n ) 1, 0.330 mmol; n ) 4, 0.0266 mmol) in 10 mL of THF
was added 1-(trimethylsilyl)imidazole (n ) 1, 319 µL, 2.178
mmol; n ) 4, 206 µL, 1.406 mmol; 10% excess). The mixture
was stirred for 1 h at room temperature and then evaporated
to dryness. The resulting oil was washed with a THF/ether
(1/10) mixture to give dendrimers 16-[Gn ] as unstable powders,
extremely sensitive to moisture.
16-[G1]: Yellow powder. 54% yield. 31P {1H} NMR (THF-
d8) δ 43.4, 49.5. 1H NMR (THF-d8) δ 3.5 (d, J ) 11.4 Hz, 9
H), 7.1 (br s, 6 H), 7.3 (dd, J ) 8.5 Hz, J ) 1.6 Hz, 6 H), 7.4
(br s, 6 H), 7.6 (d, J ) 8.5 Hz, 6 H), 7.9 (br s, 6 H), 8.0 (d, J )
1.9 Hz, 3 H). 13C {1H} NMR (THF-d8) δ 31.2 (d, J ) 14.3 Hz),
120.9 (d, J ) 7.7 Hz), 120.8 (d, J ) 5.2 Hz), 129.0, 131.9 (d, J
) 13.4 Hz), 132.7, 140.4 (d, J ) 5.3 Hz), 142.5 (d, J ) 14.4
Hz), 152.1 (d, J ) 7.4 Hz).
14-[G7]: White powder: Mp 122 °C dec. 94% yield. 31P
{1H} NMR (CDCl3) δ 61.7 (br s), 68.5. 1H NMR (CDCl3) δ 3.1
(d, J ) 9.4 Hz, 576H), 3.2 (m, 567H), 3.4 (m, 384H), 3.5 (m,
768H), 5.0 (m, 768H), 5.7 (m, 384H), 7.1-7.7 (m, 1905H). 13C
{1H} NMR (CDCl3) δ 30.8 (d, J ) 10.9 Hz), 32.9 (d, J ) 13.0
Hz), 43.7, 115.3, 121.4 (br s), 127.4, 128.1, 128.2, 132.0, 132.7,
135.8 (d, J ) 15.6 Hz), 136.0 (d, J ) 7.2 Hz), 139.0 (m), 150.5
(d, J ) 6.7 Hz), 151.0 (m). IR (KBr): 3369 (m, νNH) cm-1. Anal.
Calcd for C4200H5352N1146O381P382S382
: C, 49.42; H, 5.29; N,
15.73. Found: C, 49.18; H, 5.14; N, 15.41.
Gen er a l P r oced u r e for th e Syn th esis of Den d r im er s
15-[G1], 15-[G4]. To a solution of 0.300 g of dendrimer 1-[Gn ]
(n ) 1, 0.330 mmol; n ) 4, 0.0266 mmol) in 10 mL of THF
was added a solution of triethylamine (n ) 1, 276 µL, 1.98
mmol; n ) 4, 178 µL, 1.278 mmol) and propargylamine (n )
1, 136 µL, 1.98 mmol; n ) 4, 88 µL, 1.278 mmol) in 10 mL of
THF. The mixture was stirred for 12 h at room temperature.
The precipitate was eliminated by centrifugation, and then the
solution was evaporated to dryness. The resulting powder was
purified by column chromatography on silica gel (eluent: ethyl
acetate).
16-[G4]: Yellow powder. 45% yield. 31P {1H} NMR (THF-
d8) δ 43.1, 49.8, 59.4, 59.9, 60.1. 1H NMR (THF-d8) δ 3.3-3.5
(m, 135 H), 7.1 (br s, 48 H), 7.2-8.0 (m, 321 H). 13C {1H} NMR
(THF-d8) δ 31.3 (d, J ) 12.6 Hz), 32.5-33.1 (m), 120.9 (d, J )
7.4 Hz), 122.1 (br s), 128.5, 128.7, 131.9 (d, J ) 13.5 Hz),
132.9-133.1 (m), 140.4 (d, J ) 4.3 Hz), 142.5 (d, J ) 12.7 Hz),
142.8 (d, J ) 13.1 Hz), 151.0-152.0 (m), 152.5 (d, J ) 7.9 Hz).
15-[G1]: Yellow powder. Mp 39 °C dec. 93% yield. 31P {1H}
NMR (CDCl3) δ 52.8, 67.5. 1H NMR (CDCl3) δ 2.24 (t like, J
) 2.5 Hz, 6 H), 3.33 (d, J ) 9.8 Hz, 9 H), 3.53 (q like, J ) 6.5
Hz, J ) 6.6 Hz, J ) 6.7 Hz, 6 H), 3.83 (dddd, J ) 17.7 Hz, J
J O960045B