One-step surface decoration of poly(propyleneimines) (PPIs) with the glyceryl moiety: New way for recycling homogeneous dendrimer-based catalysts

Article abstract of DOI:10.1002/adsc.201000229

First to fifth generations of poly(propy-leneimines) (PPIs) were reacted with glycerol carbonate yielding a new family of glycerol-decorated PPIs (GD-PPI). Owing to the presence of glyceryl units surrounding the PPI core, the high generation GD-PPI-5 can be successfully immobilized in a glycerol phase, thus offering a convenient route for possible utilization as a recyclable homogeneous catalyst. In this context, we show here that GDPPI-5 can be used as a basic catalyst in the ring opening of epoxides with carboxylic acids in glycerol. The high affinity of GD-PPI-5 for the glycerol phase allowed us to (i) selectively extract the reaction products from the glycerol/GD-PPI-5 mixture and (ii) recycle the GD-PPI-5 catalyst. More generally, this work offers new tools for the convenient recycling of valuable but expensive dendrimers.

Full text of DOI:10.1002/adsc.201000229

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DOI: 10.1002/adsc.201000229
One-Step Surface Decoration of Poly(propyleneimines) (PPIs)
with the Glyceryl Moiety: New Way for Recycling Homogeneous
Dendrimer-Based Catalysts
Sꢀbastien Balieu,a Anji El Zein,a Rodolphe De Sousa,b FranÅois Jꢀrꢁme,b,*
Arnaud Tatibouꢂt,c Sylvain Gatard,a Yannick Pouilloux,b Joꢂl Barrault,b
Patrick Rollin,c and Sandrine Bouquillona,*
a
Institut de Chimie Molꢀculaire de Reims, UMR CNRS 6229, Universitꢀ Reims-Champagne-Ardenne, UFR Sciences, BP
1039 boꢃte 44, 51687 Reims Cedex 2, France
Fax : (+33)-(0)3-2691-3166; phone: (+33)-(0)3-2691-8973; e-mail: sandrine.bouquillon@univ-reims.fr
Laboratoire de Catalyse en Chimie Organique, UMR 6503 CNRS-Universitꢀ de Poitiers 40, avenue du recteur Pineau,
b
86022 Poitiers Cedex, France
Fax : (+33)-(0)5-4945-3349; phone: (+33)-(0)5-4945-4052; e-mail: francois.jerome@univ-poitiers.fr
ICOA, UMR 6005, UFR Sciences Universitꢀ d’Orlꢀans- BP 6759 rue de Chartres, 45067 Orlꢀans Cedex 2, France
c
Received: March 24, 2010; Revised: June 28, 2010; Published online: August 16, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201000229.
Abstract: First to fifth generations of poly(propy-
ACHTUNGTRENNUNGleneimines) (PPIs) were reacted with glycerol car-
hybrid organic-inorganic polymers.[3] More recently,
immobilization of homogeneous catalysts in a liquid
phase has emerged as a feasible approach. In this con-
text, ionic liquids,[4] polyethylene glycol[5] and fluorous
solvents[6] have been widely investigated. Although
fascinating works have been reported, these solvents
have shortcomings such as high cost or toxicity.
Within the framework of green chemistry, the utiliza-
tion of water as a liquid phase for homogeneous cata-
lyst immobilization has received considerable interest
and elegant works have already emerged in the litera-
ture.[7]
Recently, we and others have reported that glycerol
presents close similarities with water.[8] Indeed, like
water, glycerol is naturally available, cheap and can
be used as an environmentally friendly solvent for
catalysis and organic chemistry. Like water, glycerol is
poorly miscible with most of the organic solvents al-
lowing a convenient extraction of the reaction prod-
ucts. Interestingly, glycerol is able to dissolve more
hydrophobic substrates than water, thus offering a
good means for the immobilization of a wider range
of homogeneous catalysts. For an efficient immobili-
zation in glycerol, the homogenous catalyst has to
meet different criteria such as (i) have a high polarity
bonate yielding a new family of glycerol-decorated
PPIs (GD-PPI). Owing to the presence of glyceryl
units surrounding the PPI core, the high generation
GD-PPI-5 can be successfully immobilized in a
glycerol phase, thus offering a convenient route for
possible utilization as a recyclable homogeneous
catalyst. In this context, we show here that GD-
PPI-5 can be used as a basic catalyst in the ring
opening of epoxides with carboxylic acids in glycer-
ol. The high affinity of GD-PPI-5 for the glycerol
phase allowed us to (i) selectively extract the reac-
tion products from the glycerol/GD-PPI-5 mixture
and (ii) recycle the GD-PPI-5 catalyst. More gener-
ally, this work offers new tools for the convenient
recycling of valuable but expensive dendrimers.
Keywords: catalyst immobilization; dendrimers;
glycerol carbonate; glycerol-decorated dendrimers;
green solvent
The recovery of homogeneous catalysts represents a in order to ensure a strong interaction with the glycer-
very important issue in academia and in industry. To ol phase and (ii) have a chemical inertia towards glyc-
date many strategies have been reported such as the erol. In this context, dendrimers represents an attrac-
covalent grafting of homogeneous catalysts on a solid tive class of homogeneous catalyst for our purpose.[9]
support,[1] their non-covalent immobilization[2] and Indeed, despite promising catalytic properties, the
their encapsulation within organic, inorganic or high prices of dendrimers represent today the main
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Adv. Synth. Catal. 2010, 352, 1826 – 1833

One-Step Surface Decoration of Poly(propyleneimines) (PPIs) with the Glyceryl Moiety
limitation for their wide utilization in industry and phase extraction with ethyl acetate.[10] Although the
academia. Therefore, the search for innovative con- PPI-5 is highly polar, PPI-5 was unfortunately co-ex-
cepts that are capable of recycling this valuable but tracted with the reaction products. Therefore, during
expensive homogeneous catalyst is highly worthwhile. the recycling experiments, a significant drop in yield
Among dendrimers, PPIs are of prime importance. was observed and only a 21% yield of ester was ob-
Owing to their high polarity, PPIs are soluble in glyc- tained after the 4th catalytic run (Table 1).
erol while the presence of weakly basic amino groups,
In order to circumvent this issue and to assure a
which are unable to deprotonate glycerol, may act as better immobilization of PPI in the glycerol phase, we
basic catalytic sites. Here, we wish to report that the decided to decorate the PPIs with glycerol moieties.
decoration of PPIs with glycerol moieties allowed As we had functionalized P- or Si-based dendrimers
their convenient immobilization in glycerol, thus of- with pentoses or pentoses derivatives[11] we attempted
fering a promising tool for (i) conveniently separating the functionalization of PPI dendrimers with glycerol
the reaction products from the glycerol/dendrimers units using glycerol carbonate as an organic building
catalytic phase and (ii) allowing the recycling of these block. In the existing literature, it has been clearly es-
glycerol-decorated PPIs (GD-PPI). In particular, we tablished that primary amines readily reacted with
showed that there exists a close relationship between glycerol carbonate to generate a glyceryl carbamate
the generation of the GD-PPIs and their immobiliza- moiety.[12] In particular, this strategy is a safe and se-
tion in the glycerol phase.
lective way to introduce a glyceryl unit onto a poly-
In a first set of experiments, we investigated the mer backbone. Inspired by these works, different gen-
base-catalyzed ring opening of 1,2-epoxydodecane erations of GD-PPIs were prepared by reaction of
with dodecanoic acid in glycerol. For the above stated PPIs with glycerol carbonate.
reasons, the fifth generation PPI-5 was first tested as
The first generation GD-PPI-1 was obtained by re-
a homogeneous catalyst. In a typical procedure, an action of the terminal secondary amines of a first gen-
equimolar mixture of 1,2-epoxydodecane and dodeca- eration PPI (named PPI-1) with glycerol carbonate
noic acid (1 mmol) was heated in 4 mL of glycerol at (Table 2). In a mixture THF/DMF, no reaction occurs
1108C and in the presence of 0.2 equiv. (based on the due to the insolubility of the starting dendrimer (PPI-
amount of nitrogen) of PPI-5. As summarized in the 1) in such a mixture of solvents (Table 2, entry 1).
Table 1, PPI-5 was able to catalyze the ring opening Thus, we chose MeOH as solvent in which both the
of 1,2-epoxydodecane with dodecanoic acid in glycer- PPI-1 and the glycerol carbonate are highly soluble.
ol leading to a 69% yield of the desired esters after The reaction of PPI-1 with one equivalent of glycerol
4 h of reaction. The selectivity to the desired ester carbonate (with respect to the primary amines of PPI-
was not exclusive (75%) due to (i) the thermal degra- 1) in MeOH led to 85% conversion of glycerol car-
dation of the 1,2-epoxydodecane and (ii) the probable bonate within 24 h (Table 2, entry 2). Note that the
ring opening of the 1,2-epoxydodecane by the amino reaction proceeds here at room temperature illustrat-
groups of the PPI-5.
ing the high reactivity of glycerol carbonate. When
At the end of the reaction, the products were easily the amount of glycerol carbonate was slightly in-
recovered from the glycerol phase by liquid-liquid creased from 1.0 to 1.1 equiv., the conversion was in-
creased up to 95% (Table 2, entry 3).
The reaction of PPI-1 with glycerol carbonate was
clearly evidenced by H NMR especially focussing on
the chemical shift of the protons H-5 corresponding
Table 1. Ring opening of 1,2-epoxydodecane with dodecano-
ic acid catalyzed by PPI-5 in glycerol.
1
À
À
to the CH2 NH2 group (2.7 ppm for PPI-1 and
3.14 ppm for PPI-GD1, see Experimental Section).
1
While H NMR confirmed the formation of GD-PPI-
1 with a glycerol carbonate conversion of 95%, mass
spectrometry (MS-MS analysis) revealed the non-neg-
ligible presence of a secondary product corresponding
to the grafting of only three glyceryl units on the PPI-
1. The purification of GD-PPI-1 was performed by
solubilizing the crude mixture in a minimum of
MeOH. To our delight, upon addition of pentane/
ethyl acetate (2/1), the GD-PPI-1 precipitated as a
pure product. After this purification step, the GD-
PPI-1 was isolated with 78% yield.
Entry Catalytic
cycle[a]
Epoxide conversion Isolated yield
[%]
[%]
1
2
3
4
1
2
3
4
92
69
48
41
69
45
29
21
Proceeding on the same lines, higher generations of
GD-PPIs were prepared (Table 3). Using the same
conditions as those described above for GD-PPI-1,
[a]
All reactions were stopped after 4 h.
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Table 2. Reaction conditions for the synthesis of GD-PPI-1.
Entry
Equiv. glycerol carbonate[a]
Solvent
Time [h]
Conv. [%]
1
2
4
1.1
1.0
1.1
THF/DMF
MeOH
MeOH
96
24
7
0
85
>95
[a]
Amount of glycerol carbonate per amino group.
Table 3. Reaction conditions for the synthesis of GD-PPI-2–GD-PPI-5 in MeOH.
Entry PPI
Equiv. Glycerol carbonate[a] Equiv. Et3N Temp. [8C] Time [h] Product
Conv. [%] Yield [%][b]
1
2
3
4
5
6
7
PPI-2 1.1
–
r.t.
r.t.
r.t.
r.t.
65
24
24
44
68
24
24
24
GD-PPI-2 76
GD-PPI-2 96
GD-PPI-3 76
GD-PPI-3 85
GD-PPI-3 98
GD-PPI-4 99
GD-PPI-5 98
–
87
–
PPI-2 1.1
PPI-3 1.1
PPI-3 1.2
PPI-3 2.5
PPI-4 2.5
PPI-5 2.5
0.7
0.7
0.7
2.5
2.5
2.5
–
80
73
95
65
65
[a]
[b]
Equivalent of glycerol carbonate was calculated on the basis of -NH2 group of PPI.
Isolated yields.
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One-Step Surface Decoration of Poly(propyleneimines) (PPIs) with the Glyceryl Moiety
Scheme 1. Structures of GD-PPI-1–GD-PPI-5 synthesized in this work.
the synthesis of the second generation GD-PPI-2 led rification by precipitation, the corresponding GD-
only to 76% conversion of glycerol carbonate at room PPI-3 was isolated with 80% yield. These optimal
temperature (Table 3, entry 1). This lower conversion conditions were also applied with success to the prep-
is probably due to the higher steric hindrance of PPI- aration of GD-PPI-4 and GD-PPI-5 which were iso-
2. We found that addition of triethylamine to the re- lated with 73 and 95% yields, respectively (Table 3,
action medium allowed a significant increase in the entries 6 and 7). In the Scheme 1 is represented the
glycerol carbonate conversion from 76 to 96% structure of the GD-PPI-1–GD-PPI-5 prepared in this
(Table 3, entry 2 vs. entry 1). Here again, the reaction work.
of PPI-2 with glycerol carbonate was monitored by
The above-described GD-PPI-1–GD-PPI-5 were
1H NMR where a shift of 0.4 ppm of the protons H-8 then tested as homogeneous catalyst in the ring open-
(2.7 ppm for PPI-2 and 3.12 ppm for GD-PPI-2, see ing of 1,2-epoxydodecane with dodecanoic acid in
Experimental Section) was observed. After purifica- glycerol. As summarized in Table 4, all GD-PPI-1–
tion by precipitation, the second generation GD-PPI- GD-PPI-5 were found to be 2.5 times less active than
2 was isolated with 87% yield (Table 3, entry 2).
the reference homogeneous catalyst PPI-5 while the
Synthesis of the higher generation of GD-PPI was selectivity of the reaction remained similar. This de-
more complex and the reaction conditions had to be crease of activity might be ascribed to (i) the greater
adapted. Using the above-described procedure for the hydrophylicity of GD-PPIs as compared to that of
synthesis of GD-PPI-3, the conversion of glycerol car- PPI-5 making more difficult their interaction with re-
bonate reached only 76% (Table 3, entry 3). Increas- actants and (ii) the more difficult accessibility of the
ing the amount of glycerol carbonate from 1.1 to nitrogen atoms. It should be noted that no difference
1.2 equiv. resulted in an increase of the glycerol car- of activity was observed between all tested GD-PPIs.
bonate conversion from 76% to 85% (Table 3,
Interestingly, on the basis of the kinetic profiles, we
entry 4). Finally, by using a larger amount of glycerol found that an induction period was necessary
carbonate (2.5 equiv.) while refluxing the mixture for (Figure 1). Indeed, after nearly 30 min of reaction at
24 h in methanol, the conversion of glycerol carbon- 1108C, the reaction rate was significantly increased.
ate was nearly complete (Table 3, entry 5). After pu- This effect is even more pronounced when the reac-
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Table 4. Ring opening of 1,2-epoxydodecane with dodecano-
ic acid catalyzed by PPI-GD1–GD-PPI-5 in glycerol.
Next, we examined the influence of the decoration
of PPIs with glycerol moieties on their immobilization
in glycerol. To this end, recycling experiments were
performed. In all experiments, products of the reac-
tion were recovered by liquid-liquid phase extraction
with ethyl acetate and reactants were directly reload-
ed to the glycerol phase. All reactions were stopped
after 4 h of reaction.
From Figure 2, it clearly appears that the GD-PPIs
are much more retained in the glycerol phase than
PPI-5, thus validating our strategy. Interestingly, the
recyclability of the GD-PPIs is closely dependent on
their generation. Indeed, increasing the generation of
GD-PPIs resulted in a better immobilization in the
Entry
Catalyst
Time [h]
Conv. [%]
Yield [%][a]
1
2
3
4
5
6
7
–
4.0
4.0
7.5
7.5
7.5
7.5
7.5
30
92
95
95
95
94
95
12
69
71
71
72
70
73
PPI-5
GD-PPI-1
GD-PPI-2
GD-PPI-3
GD-PPI-4
GD-PPI-5
[a]
Isolated yields.
tion temperature was decreased to 908C. At this tem- glycerol phase. In particular, the high generation GD-
perature, the induction period was about 4 h. We PPI-5 was strongly retained in the glycerol phase, thus
assume that this period of induction corresponds to allowing a convenient recycling of the catalyst. As il-
the formation of an acid-base ion pair between the lustrated in Figure 2, the GD-PPI-5 catalyst was suc-
amino groups of the GD-PPI and the dodecanoic cessfully recycled at least 5 times without an obvious
acid. Then the corresponding carboxylate of ammoni- loss of activity. Note that elemental analysis of the re-
um plays the role of a phase-transfer agent and accel- covered ester revealed the absence of nitrogen further
erates the dissolution of the reactants in the catalytic confirming that GD-PPI-5 was left in the glycerol
glycerol phase. Such a phenomenon can be also ob- phase after the liquid-liquid phase extraction.
served visually. Indeed, after 30 min of reaction, the
Having this GD-PPI-5 in hand, we then tested dif-
reaction medium becomes turbide in accordance with ferent acids and epoxides in order to check the versa-
the formation of an emulsion (Figure 1).
Figure 1. Catalytic activity of GD-PPI-5 at 1108C and 908C. Pictures were taken at 1108C after stopping of the reaction stir-
ring.
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One-Step Surface Decoration of Poly(propyleneimines) (PPIs) with the Glyceryl Moiety
cycling these valuable but expensive dendrimeric-
based homogeneous catalysts.
Experimental Section
Solvents were distilled and dried under argon. The THF was
dried over sodium/benzophenone and the MeOH over
sodium. All other commercial products are used as received
without further purification. TLC were performed on silica
60 F254 Fluka and chromatographies on SDS silica 60 ꢅ
1
(0.060–0.200 mm). H and 13C NMR spectra were recorded
on an AC 250 Bruker in CDCl3 or DMSO-d6 as solvents
1
with TMS as reference for H spectra and CDCl3 (d=77.0)
or DMSO-d6 (d=39.8) for 13C{1H} spectra. IR spectra were
recorded on an AVATAR 320 FT-IR apparatus (KBr pellets
or films). Elemental analysis (C, H, N) were realized on a
Flash EA-1112 Series.
Figure 2. Recycling experiments.
All experiments (MS and HR-MS) were performed on a
hybrid tandem quadrupole/time-of-flight (Q-TOF) instru-
ment, equipped with a pneumatically assisted electrospray
(Z-spray) ion source (Micromass, Manchester, UK) operat-
ed in the positive mode. The electrospray potential was set
to 3 kV in the positive ion mode (flow of injection
5 mLminÀ1.) and the extraction cone voltage was usually
varied between (30–90 V).
tility of our catalytic system. Results are summarized
in the Table 5.
Whatever the considered epoxide or carboxylic
acid, the homogeneous catalyst GD-PPI-5 afforded,
in glycerol, the corresponding esters with a yield
range of 45–70%. To our great delight, in all cases,
the esters were selectively extracted from the catalytic
phase by liquid-liquid phase extraction with ethyl ace-
tate, thus allowing us to recycle the homogeneous cat-
alyst GD-PPI-5 at least 3 times without an apprecia-
ble change of activity.
In conclusion, we have reported here the synthesis
of new dendrimers that can be successfully immobi-
lized in glycerol. We found that the high generation
of glycerol-decorated PPIs can be successfully immo-
bilized in sustainable and cheap glycerol, thus offering
new tools for (i) selectively extracting the reaction
products from the glycerol/catalyst phase and (ii) re-
General Procedure for Catalytic Experiments
Typically, epoxide (1 mmol) and carboxylic acid (1 mmol)
were mixed in 4 mL of glycerol in the presence of the de-
sired GD-PPI (amount of catalytic basic sites introduced:
0.2 equiv. of nitrogen atoms). The resulting mixture was
then stirred at 1108C up to total consumption of the epox-
ide. At the end of the reaction, the reaction products were
directly extracted with ethyl acetate. After evaporation
under reduced pressure, the recovered residue was purified
over flash silica gel chromatography using a mixture of hep-
Table 5. Generalization of the catalytic process.
Entry
1
Epoxide
Carboxylic acid
Catalytic run
Yield [%][a]
1
2
3
1
2
3
1
2
3
1
2
3
71
64
69
66
65
62
44
43
45
50
47
46
2
3
4
[a]
Isolated yields.
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Sꢀbastien Balieu et al.
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tane/ethyl acetate (80/20) as eluent. Analytical data of prod-
ucts are provided in the Supporting Information.
Data for GD-PPI-3
General Procedure for the Catalyst Recycling
At the end of the reaction, the reaction products were ex-
tracted from the glycerol/catalytic phase with ethyl acetate
(1ꢆ4 mL). Then, 1 mmol of epoxide and 1 mmol of carbox-
ylic acid were reloaded. In all recycling experiments, the re-
action was stopped after the same reaction time.
C152H304N30O64: MW 3576 gmolÀ1; yield: 80%; 1H NMR
(250 MHz, DMSO-d6, 298 K): d=1.40 (4H, s, H-1), 1.64
(56H, m, H-4+H-7+H-10), 2.49 (84H, s, H-2+H-3+H-5+
H-6+H-8+H-9), 3.14 (32H, m, H-11), 3.62 (20H, m, H
glycerol moiety), 4.01 (36H, m, H glycerol moiety), 4.84
(32H, m, H glycerol moiety), 7.21 (16H, m, NHCO);
13C NMR (62.5 MHz, DMSO-d6, 298 K): d=24.9, 25.0, 28.0,
51.7, 52.2, 53.0, 61.1, 63.8, 64.0, 66.4, 70.7, 73.4, 76.2, 157.1,
157.3; MS: m/z=3568.2, calcd. for C152H305N30O64 [M+H+]:
3575.1; elemental analysis calcd. (%) for C152H108N30O64: C
51.05, H 8.57, N 11.75; found: C 50.25, H 8.82, N 11.54.
General Procedure for the Synthesis of GD-PPI
To a solution of PPI dendrimer (1.0 equiv.) in MeOH
(2 mL) were added glycerol carbonate (1.25 equiv. per
branch) and triethylamine (1.25 equiv. per branch). After
stirring the mixture under reflux overnight, the solvent was
removed under reduced pressure. The crude product was
dissolved in a minimum volume of MeOH, then precipitated
with excess of pentane/AcOEt (2:1, v/v). Glycerodendrimers
were obtained as pale yellow oils in 78, 87, 80, 73 and 95%
yields for GD-PPI-1, GD-PPI-2, GD-PPI-3, GD-PPI-4 and
GD-PPI-5 respectively.
Data for GD-PPI-4
Data for GD-PPI-1
C312H624N62O128: MW 7293 gmolÀ1; yield: 73%; 1H NMR
(250 MHz, DMSO-d6, 298 K): d=1.40 (124H, s, H-1+H-4+
H-7+H-10+H-13), 2.25 (180H, s, H-2+H-3+H-5+H-6+
H-8+H-9+H-11+H-12), 2.87 (64H, m, H-14), 3.60 (148H,
m, H glycerol moiety), 4.60 (76H, m, H glycerol moiety),
6.94 (32H, m, NHCO); 13C NMR (62.5 MHz, DMSO-d6,
298 K): d=24.4, 24.5, 27.4, 51.4, 51.7, 52.1, 52.2, 60.5, 63.2,
63.5, 65.9, 70.2, 72.9, 75.7, 156.3, 156.8; elemental analysis
calcd. (%) for C312H624N62O128: C 51.39, H 8.62, N 11.97;
found: C 50.34, H 8.68, N 11.79.
C32H64N6O16: MW 788.88 gmolÀ1
;
yield: 78%; 1H NMR
(250 MHz, DMSO-d6, 298 K): d=1.29 (4H, s, H-1), 1.47
(8H, s, H-4), 2.29 (12H, s, H-2+H-3), 2.93 (8H, m, H-5),
3.40 (10H, m, H glycerol moiety), 3.88 (8H, m, H glycerol
moiety), 4.55 (10H, m, H glycerol moiety), 7.03 (4H, m,
NHCO); 13C NMR (62.5 MHz, DMSO-d6, 298 K): d=25.9,
27.5, 51.4, 53.8, 60.5, 63.2, 63.5, 65.9, 70.2, 75.7, 156.5, 156.8;
HR-MS: m/z=789.4459, calcd. for C32H65N6O16 [M+H+]:
789.5547; elemental analysis calcd. (%) for C32H64N6O16: C
48.72, H 8.18, N 10.65; found: C 48.47, H 8.24, N 10.36.
Data for GD-PPI-5
Data for GD-PPI-2
C632H1200N126O256: MW 14661 gmolÀ1; yield: 95%; 1H NMR
(250 MHz, DMSO-d6, 298 K): d=1.34 (252H, s, H-1+H-4+
H-7+H-10+H-13+H-16), 2.18 (372H, s, H-2+H-3+H-5+
H-6+H-8+H-9+H-11+H-12+H-14+H-15), 2.87 (128H,
m, H17), 3.60 (224H, m, H glycerol moiety), 4.60 (224H, m,
H glycerol moiety), 6.94 (64H, m, NHCO); 13C NMR
(62.5 MHz, DMSO-d6, 298 K): d=25.7, 25.8, 28.8, 28.9, 53.0,
53.2, 53.5, 53.5, 53.6, 53.8, 53.9, 62.1, 64.8, 65.1, 67.5, 71.8,
74.5, 77.2, 158.1, 158.4; elemental analysis calcd. (%) for
C632H1264N126O256: C 51.53, H 8.66, N 11.99; found: C 51.72,
H 8.73, N 12.53.
C72H144N14O32: MW 1718 gmolÀ1
;
yield: 87%; 1H NMR
(250 MHz, DMSO-d6, 298 K): d=1.29 (4H, s, H-1), 1.47
(24H, m, H-4+H-7), 2.30 (36H, s, H-2+H-3+H-5+H-6),
2.96 (16H, m, H-8), 3.40 (20H, m, H glycerol moiety), 3.89
(12H, m, H glycerol moiety), 4.50 (24H, m, H glycerol
moiety), 7.01 (8H, m, NHCO); 13C NMR (62.5 MHz,
DMSO-d6, 298 K): d=24.4, 24.9, 27.4, 51.7, 52.1, 53.8, 60.5,
61.0, 63.2, 63.5, 65.9, 66.3, 70.2, 72.9, 75.6, 77.4, 156.5, 156.8;
MS: m/z=1713.6, calcd. for C72H145N14O32 [M+H+]: 1718.0;
elemental analysis calcd. (%) for C72H144N14O32: C 50.34, H
8.45, N 11.41; found: C 49.69, H 8.40, N 10.79.
1832
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Adv. Synth. Catal. 2010, 352, 1826 – 1833

One-Step Surface Decoration of Poly(propyleneimines) (PPIs) with the Glyceryl Moiety
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This work was supported by the CPER framework (Pentoraf
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pagne-Ardenne and FEDER for material funds and fellow-
ship to S.B. The authors also acknowledge the CNRS and
French Ministry of Research for their financial support. RDS
is also grateful to the Agence National de la Recherche
(action no. ANR-07-CP2D-07-02) for his PhD grant.
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