First phosphorous d-xylose-derived glycodendrimers

Article abstract of DOI:10.1016/j.tetlet.2009.02.015

Phosphorous glycodendrimers have been prepared in quantitative yields by grafting xylose-derived moieties on phosphorous dendrimers involving hydrazone units. These dendrimers could be hydrophobic or amphiphilic, respectively, with acetylated or unprotect

Full text of DOI:10.1016/j.tetlet.2009.02.015

Tetrahedron Letters 50 (2009) 1902–1905
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Tetrahedron Letters
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First phosphorous D-xylose-derived glycodendrimers
Caroline Hadad a, Jean-Pierre Majoral b,c, Jacques Muzart a, Anne-Marie Caminade b,c, Sandrine Bouquillon a,
*
a Institut de Chimie Moléculaire de Reims, CNRS UMR 6229, Université de Reims Champagne-Ardenne, BP 1039, 51687 Reims Cedex, France
b CNRS, LCC (Laboratoire de Chimie de Coordination), 205, Route de Narbonne, F-31077 Toulouse, France
c Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Phosphorous glycodendrimers have been prepared in quantitative yields by grafting xylose-derived moi-
eties on phosphorous dendrimers involving hydrazone units. These dendrimers could be hydrophobic or
amphiphilic, respectively, with acetylated or unprotected sugar moieties.
Ó 2009 Elsevier Ltd. All rights reserved.
Received 17 December 2008
Revised 30 January 2009
Accepted 3 February 2009
Available online 8 February 2009
For several years now, we have been involved in a research pro-
gramme dedicated to the valorization of pentoses especially -xy-
lose or -arabinose, now readily accessible from wheat straw and
sponding to the core P atom and the other to the P1 atom (Scheme
3). In GC1, the chemical shifts of P core and P1 are, respectively,
62.75 and 8.55 ppm. When substitution of one Cl or two Cl oc-
curred, the chemical shift of P core is not modified while the chem-
ical shifts of P1 are, respectively, 68.5 or 63.5 ppm.
D
L
bran.1 We have previously transformed pentoses into amphiphilic
structures.2 Since a short time, we have studied the possibility to
synthesize some glycodendrimers involving pentose moieties by
grafting pentose-derived moieties on phosphorous dendrimers.
Glycodendrimers have been recently developed for potential use
in micellar enantioselective catalysis3 or in pharmaceutical field
or in nanotechnology.4
At first, nitrogen-containing bases such as Et3N, TMEDA or DBU
in different ratios with respect to the Cl atoms (respectively, 2, 1.25
and 1.25) were used in THF or CH2Cl2. Temperatures were adjusted
at room temperature or allowed to rise from 0 °C to rt and reaction
times varied from 5 to 12 h. Unfortunately, each reaction led to
mono- and disubstitution adducts with degradation products of
starting phosphorous dendrimer proved by many 31P NMR signals.
Next, inorganic bases such as NaH, K2CO3 and Cs2CO3 were
used under different conditions: with NaH (2 equiv/Cl atom),
the disubstitution compound is observed but always with degra-
dation products of GC1. No influence of the temperature has also
been proved by maintaining this one at 0 or ꢀ10 °C during the
entire reaction. The addition of 2 equiv of K2CO3 per chloride
atom led exclusively to the formation of the monosubstitution
adduct with few degradation products. Finally, reactions with
Cs2CO3 were achieved at various temperatures (0 °C to rt), this
inorganic base being more soluble in organic solvents than most
carbonates such as potassium carbonate. These reactions led to
disubstitution and degradation products but 31P NMR spectra
seemed to be cleaner than previously observed. So, we explored
the possibility of using a large excess of this base in the pres-
ence of GC1 at first and next, the nucleophilic species 1 was
added. This experiment was concluding because only the disub-
stitution compound was observed without degradation of the
starting material.
Phosphorous starting dendrimers involving hydrazone units
were prepared as previously described using a two step route
(Scheme 1).5
Substitution of the chloride atoms of PSCl2 unit could be
attempted by amines,6 phenolic entities branched on specific pes-
ticides,7 organometallic8 or fluorophoric moieties.9 To our knowl-
edge, no sugar entities have been grafted on such dendrimers to
give phosphorous glycodendrimers that urge us to publish our
study.
At first, we attempted the direct coupling of 2,3,4-tri-O-acetyl-
D-
xylopyranose10 or 20-hydroxyethyl-2,3,4-tri-O-acetyl-b-
D-xylopy-
ranoside11 with GC1 without success. Such result is not surprising,
since no reaction with alcohols had occurred with GC1 (or higher
generations), whereas numerous reactions with phenols were suc-
cessful, as indicated above. So, we decided to prepare the triacetylat-
ed phenolic derivative of xylose 1 by glycosylation of peracetylated
xylose in the presence of a Lewis acid, BF3.Et2O (Scheme 2).12 This
compound was obtained in a moderate yield as a mixture of two
conformers and engaged in coupling reactions with phosphorous
dendrimers GC1, GC2 and GC3.
The reacting conditions were applied on GC1 using the protocol
described in Scheme 3 and the reactions were followed by 31P NMR
spectroscopy. In fact, two different peaks are observed: one corre-
We also developed a protocol of purification of the glycodendri-
mer GX113 involving only filtration and extraction steps: Excess of
Cs2CO3 is eliminated by centrifugation and the glycodendrimer is
purified from xyloside 1 traces by precipitation in a mixture of
Et2O/pentane (1:1) and obtained with 96% yield. Grafting of 12
xyloside entities was confirmed by the 1H NMR spectroscopy.
* Corresponding author.
E-mail address: sandrine.bouquillon@univ-reims.fr (S. Bouquillon).
0040-4039/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2009.02.015

C. Hadad et al. / Tetrahedron Letters 50 (2009) 1902–1905
1903
MeS
H2N N P
Cl
Cl
N
P
Cl
Cl
Cl
Cl
P
N
P
N
Cl
S
P
K2CO3
Cl
Cl
N3P3
O
CHO
+ 6
CHO
N3P3
O
CH
N N
Me
HO
6
THF, RT
CHCl3, r.t.
6
Cl
GC1
S
P O
S
P
H
H
C
Cl
Cl
C
N3P3
O
N N
N N
Me
2
2
6
6
Me
GC2
S
P O
S
P
S
P
H
C
H
C
H
C
Cl
Cl
O
N3P3
O
N N
N N
Me
N
N
2
Me
GC3
Me
Scheme 1. Synthesis of phosphorous starting dendrimers.
BF3OEt2 (2.4 eq.)
Et3N (0.7 eq.)
HO
HO
CH3COONa, 3H2O AcO
(1 eq.)
AcO
O
CH2Cl2, r.t., 24 h
O
O
acetic anhydride
OH
AcO
OAc
AcO
O
HO
OH
(1 eq.)
(12 eq.)
OH
OAc
54 %
OAc
96 %
100 °C, 24 h
1
OH
Scheme 2. Preparation of parahydroxyphenyl-2,3,4-tri-O-acetyl-b-
D-xylopyranoside, 1.
O
OAc
OAc
O
S
P1
P1 S
O
O
Base, Solvent, T(°C), t
Cl
AcO
O
P
P
N3P3
O
CH
N N
Me
N3P3
P core
O
CH
Cl
N N
6 AcO
6
P core
O
O
GC1
OAc
Me
AcO
O
GX1
AcO
6
OAc
OAc
1
OH
Scheme 3. Couplings of parahydroxyphenyl-2,3,4-tri-O-acetyl-b-
D-xylopyranoside 1 with GC1.
O
OAc
OAc
O
Cs2CO3
S
P
S
P O
O
H
AcO
(4 eq./Cl atom)
H
C
AcO
O
O
C
GC2
+
N3P3 O
N N
Me
THF, 24 h
0 °C to r.t.
N
N
AcO
O
O
O
Me
OAc
OAc
1
2
(2 eq./Cl atom)
AcO
90 %
OAc
6
GX2
OH
GC3 + 1 (2 eq./Cl atom)
Cs2CO3
(4 eq./
O
Cl atom)
THF, 24 h
0°C to r.t.
OAc
O
S
P
S
P O
S
P
O
OAc
H
C
H
H
C
AcO
O
C
N3P3
O
N N
N N
O
N N
O
O
Me
Me
OAc
Me
2
AcO
OAc
2
6
90 %
GX3
Scheme 4. Couplings of parahydroxyphenyl-2,3,4-tri-O-acetyl-b-D-xylopyranoside 1 with GC2 and GC3.

1904
C. Hadad et al. / Tetrahedron Letters 50 (2009) 1902–1905
O
OH
OH
O
S
O
O
a)
HO
O
P
N3P3
O
O
CH
GX1
N
N
O
OH
Me
GX'1
HO
6
OH
O
OH
OH
O
S
P
S
O
a)
H
C
H
C
HO
O
P O
GX2
GX3
N3P3
N N
N
N
O
O
Me
Me
OH
2
HO
OH
6
GX'2
O
OH
OH
a)
O
S
P
S
P O
S
P
O
H
C
H
H
HO
O
O
C
N3P3
O
C
N N
N N
Me
N N
O
O
Me
OH
Me
2
HO
OH
2
6
GX'3
a) MeONa (0.5 M), MeOH/CH2Cl2, RT, 12h
Scheme 5. Hydrolysis of glycodendrimers GX1, GX2 and GX3.
3. (a) Schmitzer, A. R.; Franceschi, S.; Perez, E.; Rico-Lattes, I.; Lattes, A.; Thion, L.;
Erard, M.; Vidal, C. J. Am. Chem. Soc. 2001, 123, 5956–5961; (b) Schmitzer, A.;
Perez, E.; Rico-Lattes, I.; Lattes, A. Tetrahedron: Asymmetry 2003, 14, 3719–3730.
4. Roy, R. Trends Glycosci. Glyc. 2003, 1585, 291–310; (b) Matsuoka, K.; Hatano, K.;
Terunuma, D. Nanotechnol. Carbohydr. Chem. 2006, 89–102; (c) Li, Y.; Cheng, Y.;
Xu, T. Curr. Drug Discovery Technol. 2007, 44, 246–254; (d) Touaibia, M.; Roy, R.
Mini-Rev. Med. Chem. 2007, 712, 1270–1283; (e) Cloninger, M. J. In Molecular
Recognition and Polymers; Rotello, R., Thayumanavan, S., Eds.; Wiley, 2008; pp
335–358.
This grafting method was extended to dendrimers of second
and third generation GC2 and GC3 in quantitative yields (Scheme
4).14 As for GX1, we also observed by 31P NMR besides the signals
corresponding to the internal structure, an intermediate singlet at
about 68.5 ppm, corresponding to the monosubstitution on the ter-
minal groups, which disappears to give a new singlet at 63.5 or
64.5 ppm, corresponding to the full substitution (GX2 or GX3,
respectively).
5. Launay, N.; Caminade, A.-M.; Lahana, R.; Majoral, J.-P. Angew. Chem., Int. Ed.
Engl. 1994, 33, 1589–1592.
In order to obtain amphiphilic glycodendrimers, we engaged
GX1, GX2 and GX3 into deprotection reactions. Classical conditions
for hydrolysis of acetate groups on sugar derivatives (MeONa in
MeOH/CH2Cl2)2e have been used during a short time to avoid the
decomposition of the starting materials (Scheme 5).15 Indeed, the
P–O linkages might be sensitive to these drastic conditions. How-
ever, 31P NMR displays a single signal for each phosphorous layer
confirming the integrity of the structure. The hydrolysis of all the
acetate groups is shown by 1H NMR by the total disappearance
of the acetate signal.
6. (a) Lartigue, M.-L.; Slany, M.; Caminade, A.-M.; Majoral, J.-P. Chem. Eur. J. 1996,
2, 1417–1426; (b) Launay, N.; Slany, M.; Caminade, A.-M.; Majoral, J.-P. J. Org.
Chem. 1996, 61, 3799–3805; (c) Launay, N.; Caminade, A.-M.; Majoral, J.-P. J.
Am. Chem. Soc. 1995, 117, 3282–3283.
7. Göller, R.; Vors, J.-P.; Caminade, A.-M.; Majoral, J.-P. Tetrahedron Lett. 2001, 42,
3587–3590.
8. Routaboul, L.; Vincendeau, S.; Turrin, C.-O.; Caminade, A.-M.; Majoral, J.-P.;
Daran, J.-C.; Manoury, E. J. Organomet. Chem. 2007, 692, 1064–1073.
9. Franc, G.; Mazères, S.; Turrin, C.-O.; Vendier, L.; Duhayon, C.; Caminade, A.-M.;
Majoral, J.-P. J. Org. Chem. 2007, 72, 8707–8715.
10. (a) Utille, J.-P.; Vottero, P. J. A. Carbohydr. Res. 1980, 85, 289–297; (b) Utille, J.-
P.; Gagnaire, D. Carbohydr. Res. 1982, 106, 43–57.
11. Hadfield, A. F.; Lazo, J. S.; Sartorelli, A. C. Carbohydr. Res. 1979, 77, 51.
In conclusion, we prepared the first phosphorous glycodendri-
mers derived from D-xylose in very good yields through an easy
12. Preparation of parahydroxyphenyl-2,3,4-tri-O-acetyl-b-
D
-xylopyranoside 1:
and the
1,2,3,4-tri-O-acetyl-b- -xylopyranoside (2 g, 6.29 mmol)
D
hydroquinone (693 mg, 6.29 mmol, 1 equiv) were dissolved in CH2Cl2
(20 mL) under argon. Triethylamine (0.63 mL, 4.40 mmol, 0.7 equiv) and
BF3 ꢁ OEt2 (1.9 mL, 15.08 mmol, 2.4 equiv) were then successively added
dropwise. After 24 h stirring at room temperature, the mixture was
neutralized with triethylamine until neutral pH was obtained. The crude
product was then concentrated under reduced pressure and chromatographed
on silica gel (petroleum ether/ethyl acetate: 1:4). The para-hydroxyphenyl-
purification process. The potential of using these macromolecules
in asymmetric synthesis or micellar catalysis, especially for amphi-
philic compounds, is currently under study.
References and notes
2,3,4-tri-O-acetyl-b-
96%). Mp 121 °C. ½aDꢂ ꢀ34.8 (c 1.11 CHCl3). IR (KBr): 3458 (F), 2963(f), 2880 (f),
1775 (F), 1602 (f), 1511 (m), 1442 (f), 1222 (F), 1097 (m) cmꢀ1 1H NMR
D-xylopyranoside 1 was obtained as a beige solid (2.22 g,
1. (a) Liavoga, A. B.; Bian, Y.; Seib, P. A. J. Agric. Food Chem. 2007, 55, 845–852; (b)
Sorensen, H. R.; Pedersen, S.; Vikso-Nielsen, A.; Meyer, A. S. Enzyme Microb.
Technol. 2005, 36, 773–784; (c) Fields, R.; Wilson, R.J. Eur. Pat. Appl. EP 265111
A2 19880427, 1998.; (d) Fanta, G. F.; Abbott, T. P.; Herman, A. I.; Burr, R. C.;
Doane, W. M. Biotechnol. Bioeng. 1984, 26, 1122–1125.
2. (a) Muzart, J.; Hénin, F.; Estrine, B.; Bouquillon, S. French Patent CNRS No.
0116363, PCT WO 03053987, 2001.; (b) Estrine, B.; Bouquillon, S.; Hénin, F.;
Muzart, J. Eur. J. Org. Chem. 2004, 2914–2922; (c) Estrine, B.; Bouquillon, S.;
Hénin, F.; Muzart, J. Green Chem. 2005, 7, 219–223; (d) Damez, C.; Estrine, B.;
Bessmertnykh, A.; Bouquillon, S.; Hénin, F.; Muzart, J. J. Mol. Catal. A: Chem.
2006, 244, 93–98; (e) Damez, C.; Bouquillon, S.; Harakat, D.; Hénin, F.; Muzart,
J.; Pezron, I.; Komunjer, L. Carbohydr. Res. 2007, 342, 154–162.
.
(250 MHz, CDCl3): d 2.18–2.36 (18H), 3.70 (2H), 4.40 (dd, J = 4.6, 11.9 Hz, 2H),
5.16–5.48 (8H), 6.86–7.18 (8H) ppm. 13C NMR (62.9 MHz, CDCl3): d 20.7–20.8,
61.9, 62.0, 68.5, 68.5, 70.3, 70.5, 70.8, 71.1, 99.3, 99.9, 116.1, 116.2, 118.3,
118.7, 149.5, 150.1, 152.1, 152.2, 169.5–170.1. HRMS: calcd for
[M+Na+] = 391.1005. Found for [M+Na+] = 391.1001 g molꢀ1
C17H20O9: C, 55.43; H, 5.43. Found for C, 55.27; H, 5.79.
.
Calcd for
13. Typical procedure for preparation of phosphorous glycodendrimer GX1: In
Schlenk tube was dissolved the parahydroxyphenyl-2,3,4-tri-O-acetyl-b-
a
-
D
xylopyranoside 1 (236 mg, 0.641 mmol, 24 equiv) in THF (4 mL). After cooling
the solution at 0 °C, cesium carbonate (418 mg, 1.283 mmol, 48 equiv) was

C. Hadad et al. / Tetrahedron Letters 50 (2009) 1902–1905
1905
added followed, after 10 h stirring, by the GC1 dendrimer (49 mg, 0.027 mmol).
The resulting mixture was stirred at room temperature during 14 h. Cesium
salts were eliminated by centrifugation and the floating solution was
evaporated under reduced pressure to give a yellow solid. This one was
(192H), 6.67–7.23 (276H), 7.46–7.80 (126H) ppm. 13C NMR (62.9 MHz, CDCl3):
d 21.6–21.7, 33.0, 61.9, 68.4, 70.2, 70.7, 98.2, 117.8, 121.8, 122.5, 128.3, 132.3,
140.0, 146.1, 151.2, 154.3, 169.3–169.9 ppm. 31P NMR (101.5 MHz, CDCl3): d
8.26, 62.16, 64.55 ppm. Calcd for C1152H1248N87O474P45S42: C, 51.94; H, 4.72; N,
4.57; S, 5.06. Found for C, 51.32; H, 4.61; N, 4.77; S, 4.45.
washed by
a mixture Et2O/pentane (1:1) and isolated by centrifugation.
Phosphorous glycodendrimer GX1 was therefore obtained as a yellow powder
(150.5 mg, 96%). Mp 133 °C. IR (KBr): 3417 (F), 1755 (F), 1643 (f), 1501 (m),
15. Typical procedure for preparation of phosphorous glycodendrimer GX01: To a
solution of phosphorous glycodendrimer GX1 (238 mg, 0.041 mmol) in
a
1222 (F), 1183 (m) cmꢀ1 1H NMR (250 MHz, CDCl3): d 2.03 (s, 108H), 3.22 (d,
.
MeOH/CH2Cl2 mixture (1:1) (20 ml) was added dropwise a 0.5 M NaOMe
J = 10.13 Hz, 18H), 3.50 (dd, J = 7.9, 11.9 Hz, 12H), 4.28 (dd, J = 4.7, 11.9 Hz,
12H), 4.90–5.28 (48H), 6.80–7.15 (60H), 7.51–7.69 (18H) ppm. 13C NMR
(62.9 MHz, CDCl3): d 20.6–20.7, 33.0 (d, J = 12.17 Hz), 61.9, 68.4, 70.1, 70.7,
98.9, 117.8, 121.3, 122.4, 128.3, 132.2, 138.7 (d, J = 6.9 Hz), 145.8, 151.2, 153.9,
169.3–169.9 ppm. 31P NMR (101.5 MHz, CDCl3): d 8.52, 63.49 ppm. Calcd for
C252H276N15O114P9S6: C, 52.09; H, 4.79; N, 3.62; S, 3.31. Found for C, 52.02; H,
4.84; N, 3.72; S, 3.19.
solution (1.5 mL, 0.738 mmol, 18 equiv). After 2 hours stirring at room
temperature, phosphorous glycodendrimer GX10 was precipitated and
isolated by centrifugation as a beige powder (170 mg, 96%). Mp 172 °C. IR
(KBr): 3409 (F), 1600 (F), 1501 (m), 1185 (F), 1102 (m) cmꢀ1 1H NMR
.
(250 MHz, D2O): d 3.27–3.68 (54H), 3.72–4.23 (24H), 4.90–5.15 (12H), 7.10–
7.35 (60H), 7.51–7.69 (18H) ppm. 13C NMR (62.9 MHz, D2O):
d
33.8 (d,
J = 11.9 Hz), 66.7, 70.5, 74.2, 77.3, 102.8, 118.7, 122.1, 122.9, 129.3, 133.7, 140.3
(d, J = 15.4 Hz), 146.3 (d, J = 6.6 Hz), 152.2, 156.0 ppm. 31P NMR (101.5 MHz,
D2O): d 9.10, 64.33 ppm. Phosphorous glycodendrimer GX02: Similar procedure
14. Phosphorous glycodendrimer GX2: Similar procedure as for phosphorous
glycodendrimer
xylopyranoside
GX1
with
parahydroxyphenyl-2,3,4-tri-O-acetyl-b-D-
1
(243 mg, 0.660 mmol, 48 equiv), cesium carbonate
as for phosphorous glycodendrimer GX01 with
a
0.5 M NaOMe solution
(1.05 mL, 0.508 mmol, 36 equiv) and the GX2 dendrimer (180 mg,
0.014 mmol). Phosphorous glycodendrimer GX02 was obtained as
beige
powder (136 mg, 100%). Mp 196 °C. IR (KBr): 3408 (F), 1601 (F), 1501 (m), 1186
(m), 1101 (f) cmꢀ1 1H NMR (250 MHz, D2O): d 3.25–3.50 (78H), 3.55–3.65
(430 mg, 1.320 mmol, 96 equiv) and the GC2 dendrimer (65 mg,
0.014 mmol). Phosphorous glycodendrimer GX2 was obtained as a yellow
powder (160 mg, 90%). Mp 145 °C. IR (KBr): 3418 (F), 1757 (f), 1642 (m), 1501
a
(f), 1265 (m), 1224 (m) cmꢀ1
.
1H NMR (250 MHz, CDCl3): d 2.05 (s, 216H), 3.10–
.
3.38 (54H), 3.50 (dd, J = 7.9, 11.9 Hz, 24H), 4.28 (dd, J = 4.7, 11.9 Hz, 24H), 4.90–
5.28 (96H), 6.80–7.15 (132H), 7.51–7.69 (54H) ppm. 13C NMR (62.9 MHz,
CDCl3): d 21.2, 33.5, 62.3, 68.9, 70.6, 71.2, 99.2, 118.3, 121.8, 122.2, 122.9,
128.6, 132.5, 132.8, 139.1–139.4, 146.1, 151.7, 153.3, 169.3–169.9 ppm. 31P
NMR (101.5 MHz, CDCl3): d = 8.76, 62.99, 64.55 ppm. Calcd for
C552H600N39O234P21S18: C, 51.99; H, 4.74; N, 4.28; S, 4.53. Found for C, 51.24;
H, 4.80; N, 4.32; S, 4.25. Phosphorous glycodendrimer GX3: Similar procedure as
for phosphorous glycodendrimer GX1 with parahydroxyphenyl-2,3,4-tri-O-
(48H), 3.70–3.90 (24H), 3.95–4.05 (24H), 4.90–5.00 (24H), 7.10–7.45 (132H),
7.80–8.02 (54H) ppm. 13C NMR (62.9 MHz, D2O): d 33.7–33.9, 66.7, 70.6, 74.3,
77.3, 103.0, 118.8, 122.7, 123.1, 123.2, 129.4, 133.7, 134.0, 140.1–140.4, 146.5
(d, J = 6.9 Hz), 152.5, 156.1 ppm. 31P NMR (101.5 MHz, D2O): d 9.35, 62.65,
64.64 ppm. Phosphorous glycodendrimer GX03: Similar procedure as for
phosphorous glycodendrimer GX01 with a 0.5 M NaOMe solution (0.9 mL,
0.450 mmol, 72 equiv) and the GX3 dendrimer (166 mg, 0.006 mmol).
Phosphorous glycodendrimer GX03 was obtained as a beige powder (125 mg,
100%). Mp 199 °C. IR (KBr): 3408 (F), 1604 (F), 1501 (m), 1187 (f), 1100 (f)
acetyl-b-
D-xylopyranoside
1
(197 mg, 0.535 mmol, 96 equiv), cesium
carbonate (343 mg, 1.054 mmol, 192 equiv) and the GC3 dendrimer (69 mg,
0.006 mmol). Phosphorous glycodendrimer GX3 was obtained as a yellow
powder (135 mg, 90%). Mp 150 °C. IR (KBr): 3415 (F), 1757 (F), 1642 (f), 1501
cmꢀ1 1H NMR (250 MHz, D2O): d 3.25–3.40 (174H), 3.45–4.40 (192H), 4.95–
.
5.05 (48H), 7.10–7.45 (276H), 7.81–8.12 (126H) ppm. 13C NMR (62.9 MHz,
D2O): d 33.5–33.7, 66.4, 70.3, 74.0, 77.0, 102.7, 118.5, 122.2, 122.8–123.0,
129.1–129.2, 133.6–133.7, 140.1–140.6, 146.3, 152.4–152.6, 155.8 ppm. 31P
NMR (101.5 MHz, D2O): d 8.82, 62.92, 64.43 ppm.
(m), 1266 (F), 1225 (m) cmꢀ1 1H NMR (250 MHz, CDCl3): d 1.85–2.04 (432H),
.
3.07–3.40 (126H), 3.04-3.58 (48H), 4.16 (dd, J = 3.5, 11.4 Hz, 48H), 4.86–5.28