Synthesis, Structural Analysis, and Properties of N-Alkylglucosyl(meth)acrylamides: New Reactive Sugar Surfactants

Article abstract of DOI:10.1021/jo971486d

New reactive-surfactants, N-alkylglucosylacrylamides and N-alkylglucosylmethacrylamides, are easily prepared in two steps from glucose without protection. The complete structural analysis of these compounds by 1D and 2D NMR spectroscopy shows the existence of a rotational isomerism that is strongly dependent on the steric hindrance of the carbonyl substituent: whatever the alkyl chain length, both endo and exo rotamers are observed for N-alkylglucosylacrylamides 1 while the endo rotamer is the sole species observed in the case of N-alkylglucosylmethacrylamides 2. For acrylamido derivatives 1, the exo-endo equilibrium is solvent-dependent: the endo isomer is favored in polar nonaqueous solvents (endo-exo isomeric ratio R = 70/30) while the equilibrium is shifted toward the exo rotamer in protic acidic medium (R = 50/50 in water and 80/20 in acidic medium). An intramolecular hydrogen bond is assumed to be responsible for the increased stability of the endo rotamer. Furthermore, for tetra-O-acetylated derivatives the exo rotamer becomes favored in aprotic solvents. Surface tension measurements demonstrate that N-octyl- to -tetradecyl-substituted compounds 1 and 2 are surfactants with critical micelle concentrations ranging from 1.2 × 10^-2 to 1.7 × 10^-5 mol/L.

Full text of DOI:10.1021/jo971486d

608
J . Org. Chem. 1998, 63, 608-617
Syn th esis, Str u ctu r a l An a lysis, a n d P r op er ties of
N-Alk ylglu cosyl(m eth )a cr yla m id es: New Rea ctive Su ga r
Su r fa cta n ts
Laurence Retailleau,† Annabelle Laplace,‡ He´le`ne Fensterbank,‡ and Chantal Larpent*,‡
Universite´ de Versailles-Saint Quentin en Yvelines, LRC DSM 95/ 1, SIRCOB EP CNRS 102,
45 Avenue des Etats-Unis, 78035 Versailles, France, and ENSC Rennes, Laboratoire de Chimie
Organique et des Substances Naturelles, Avenue du Ge´ne´ral Leclerc, 35700 Rennes, France
Received August 11, 1997
New reactive-surfactants, N-alkylglucosylacrylamides and N-alkylglucosylmethacrylamides, are
easily prepared in two steps from glucose without protection. The complete structural analysis of
these compounds by 1D and 2D NMR spectroscopy shows the existence of a rotational isomerism
that is strongly dependent on the steric hindrance of the carbonyl substituent: whatever the alkyl
chain length, both endo and exo rotamers are observed for N-alkylglucosylacrylamides 1 while the
endo rotamer is the sole species observed in the case of N-alkylglucosylmethacrylamides 2. For
acrylamido derivatives 1, the exo-endo equilibrium is solvent-dependent: the endo isomer is favored
in polar nonaqueous solvents (endo-exo isomeric ratio R ) 70/30) while the equilibrium is shifted
toward the exo rotamer in protic acidic medium (R ) 50/50 in water and 80/20 in acidic medium).
An intramolecular hydrogen bond is assumed to be responsible for the increased stability of the
endo rotamer. Furthermore, for tetra-O-acetylated derivatives the exo rotamer becomes favored
in aprotic solvents. Surface tension measurements demonstrate that N-octyl- to -tetradecyl-
substituted compounds 1 and 2 are surfactants with critical micelle concentrations ranging from
1.2 × 10-2 to 1.7 × 10-5 mol/L.
Sch em e 1
In tr od u ction
Supramolecular assemblies and aqueous surfactant
aggregates can enhance chemical rates, particularly in
the case of functionalized aggregates.1 Moreover, the
microenvironment provided by the aggregates can affect
the selectivity, and some enantioselective reactions have
been described in chiral surfactant aggregates.2 Never-
theless, the search for more effective systems requires
the design of new functionalized surfactants with specific,
fitted, properties.2a
We have chosen to develop a general, short synthetic
pathway to various functionalized surfactants starting
from a common reactive-surfactant precursor. This “sur-
factant synthon” includes moieties that permit the cova-
lent binding to various molecular structures, thus leading
to an array of elaborate surfactants with additional
functionalities or to amphiphilic macromolecules. One
of the main expected outcomes of this approach is the
rational control of the aggregation properties of the
resulting compound by the structure of the starting
reactive surfactant.
We present here the synthesis, the structural charac-
terization, and the surfactant behavior of a new family
of chiral reactive surfactants derived from glucose, of
general formula 1 and 2 (Scheme 1). Numerous complex
amphiphilic molecules are readily available, in one step,
from these precursors since the (meth)acrylamido sub-
stituent can act as a polymerizable group as well as a
Michael acceptor. For example, amphiphilic polymers
have been obtained by radical polymerization of com-
pounds 1 and 2,3a and surfactant cage molecules are
readily accessible by nucleophilic addition of azacrowns
(e.g., tetraazacyclotetradecane) to acrylamido compounds
1.3b Finally, these compounds have been found to be suc-
cessful for direct glucosylation of amino-latex particles.3c
* To whom correspondence should be addressed. Tel.: (33)
1-39254413. Fax: (33) 1-39254452. E-mail: chantal.larpent@chimie.
uvsq.fr.
† ENSC Rennes.
‡ Universite´ de Versailles-Saint Quentin en Yvelines.
(1) For reviews see: (a) Fendler, J . H.; Fendler, E. J . Catalysis in
Micellar and Macromolecular Systems; Academic Press: New York,
1975. (b) Fendler, J . H. Membrane Mimetic Chemistry; Wiley-Inter-
science: New York, 1982. (c) Tonellato, U. Colloids Surf. 1989, 35,
121.
(2) For example: (a) Cleij, M. C.; Mancin, F.; Scrimin, P.; Tecilla,
P.; Tonellato, U. Tetrahedron 1997, 53, 357. (b) Ueoka, R.; Matsumoto,
Y.; Moss, R. A.; Swarup, S.; Sugii, A.; Harada, K.; Kikuchi, J . I.;
Murakani, Y. J . Am. Chem. Soc. 1988, 110, 1588. (c) Matsumoto, Y.;
Ueoka, R. J . Org. Chem. 1990, 55, 5797.
(3) (a) Retailleau, L. Ph.D. Thesis, Universite´ de Rennes 1, 1993.
(b) Arleth, L.; Posselt, D.; Gazeau, D.; Larpent, C.; Zemb, T.; Mortens-
en, K.; Pedersen, J . S. Langmuir 1997, 13, 1887. (c) Richard, J .; Vaslin,
S.; Larpent, C. Eur. Pat. Appl. EP 709, 402, 1996 (to Prolabo).
S0022-3263(97)01486-2 CCC: $15.00 © 1998 American Chemical Society
Published on Web 01/22/1998

New Reactive Sugar Surfactants
J . Org. Chem., Vol. 63, No. 3, 1998 609
a
Ta ble 1. 13C NMR Da ta (75 MHz) of Com p ou n d s 1a a n d 2a in DMSO-d 6
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
2a
1a A
1a B
87.54
82.17
86.39
69.91
69.91
70.43
79.18
79.31
78.97
69.86
70.00
69.80
77.81
77.67
77.49
61.12
61.17
61.06
172.78
166.09
166.76
140.44
128.98
129.68
114.81
128.14
126.59
40.51
42.26
42.26
a
Chemical shifts δ in ppm. Assignments made from DEPT and 2D 13C-1H NMR spectra. The atoms are numbered as shown in
Scheme 2 and Figure 3.
Sch em e 2
Resu lts a n d Discu ssion
1. Syn t h esis of N-Alk ylglu cosyl(m et h )a cr yl-
a m id es 1 a n d 2. The glucosylamides 1 and 2 are
obtained in two steps from D-glucose (Scheme 1). In the
first step, glucose is reacted with the corresponding
alkylamine according to the previously described proce-
dures.4 The resulting alkylglucosylamines 3 have been
purified by recrystallization in ethanol and characterized
1
by NMR spectroscopy. Their 13C and H NMR spectra
show the presence of the two R and â anomers in DMSO
solutions.5
Compounds 1 and 2 are obtained in a second step by
amidification of the alkylglucosylamines 3. Selective
formation of amides from amino alcohols can be achieved
using specific acylating reagents6 or by performing the
signals: CH3, ethylenic sp2, and CO carbon nuclei of the
reactions directly with an excess of acyl chloride in the
methacryloyl substituent (at 20, 115, 140, and 172 ppm,
respectively), CH2 linked to nitrogen at 40 ppm (com-
pared to 46 ppm for the starting glucosylamine 3), and
glucopyranosyl carbon nuclei (61-88 ppm). The glucopy-
ranosyl carbon C2 is shielded compared to the starting
glucosylamine 3 (∆δ ∼3-4 ppm) as already observed for
other glucosylamides.8,9
presence of water.7 We have found that selective (meth)-
acryloylation of alkylglucosylamines 3 can indeed be
achieved using the latter procedure. These reactions can
also be performed in pure methanol in the presence of a
lower excess (2 equiv) of acyl chloride since methanol
competes with primary and secondary alcohols but does
not hydrolyze the acyl chloride.
The single resonance observed for carbon C1 demon-
strates that only one isomer is present in DMSO solution.
The â configuration of compounds 2a and 2d is clearly
Thus, the alkylglucosylamine 3 is reacted with 2 equiv
(or 4-5 equiv) of acryloyl or methacryloyl chloride in the
presence of sodium carbonate in methanol (or in THF-
water). TLC monitoring of the reaction shows that the
amide 1 or 2 is formed first (within 10 min to 1 h
depending on the alkyl chain length of the starting
glucosylamine and on the solvent). Bis- and poly(meth)-
acryloylated side products are formed in a second step
and observed for longer reaction times. The crude
product 1 or 2 is isolated by extraction with ethyl acetate
and purified by column chromatography on silica gel. The
reaction yields range from 50% to 60%. The purity of
compounds 1 and 2 is demonstrated by HPLC analysis.
2. Str u ctu r a l Ch a r a cter iza tion of Com p ou n d s 1
a n d 2. N-Alkylglucosyl(meth)acrylamides 1 and 2 have
been characterized by IR, NMR, and mass spectrometry.
The mass spectra (CI, NH3) are in agreement with the
proposed structures with base peaks corresponding to the
quasimolecular (M - H+) ions. The IR spectra show the
conjugated amide I and CdC stretching bands (1650 and
1610 cm-1).
1
established by the H NMR spectra, which demonstrate
the axial position of the anomeric proton H1: its chemical
shift (4.7 ppm) is close to those described for secondary
â-glucosylamides6c,7b,10 displaying a characteristic axial-
axial coupling constant with the H2 nucleus (3J H
) 9
1-H2
Hz).11 Moreover, the other H signals are in agreement
with the proposed structure (see the Experimental Sec-
tion). It is worth noticing that the R-anomer has not been
detected either during the acylation or during the treat-
ment. As already observed for other glucosylamines,6-10
the acylation leads selectively to the â-glucosylamide
probably via R/â mutarotation.
1
Owing to the restricted rotation around the amide C-N
1
bond, the absence of doubling of H and 13C resonances
demonstrates that only one rotational isomer exists in
DMSO solution. Furthermore, the glucopyranosyl 1H
and 13C resonances of compounds 2 are close to those of
secondary â-glucosylamides where the anti conformation
of the amide C-N bond has been demonstrated by the
trans H1-NH coupling constant.10 One can thus propose
that the endo isomer (with the glucose ring cis to the
carbonyl oxygen atom, Scheme 2) is the sole rotational
isomer in solution. Moreover, as already described for
other N,N-disubstituted methacrylamides, the R,â-un-
saturated methacryloyl group is expected to adopt pre-
dominantly the s-trans conformation (Scheme 2).12
1
The H and 13C NMR spectra of compounds 2a and 2d
in DMSO-d6 are in agreement with the specific meth-
acryloylation of the nitrogen atom. The 13C NMR spectra
(Table 1, Figure 1) show the following characteristic
(4) Pigman, W.; Cleveland, E. A.; Couch, D. H.; Cleveland, J . H. J .
Am. Chem. Soc. 1951, 73, 1976.
(5) Perrin, C. L.; Armstrong, K. B. J . Am. Chem. Soc. 1993, 115,
6825.
(6) (a) J oyeau, R.; Brown, E. Bull. Soc. Chim. Fr. 1982, 11, 391. (b)
Brown, E.; J oyeau, R.; Paterne, M. Tetrahedron Lett. 1977, 30, 2575.
(c) Leon-Ruaud, P.; Allainmat, M.; Plusquellec, D. Tetrahedron Lett.
1991, 32, 1557.
(7) (a) Roy, R.; Laferriere, C. A. J . Chem. Soc., Chem. Commun.
1990, 1709. (b) Kallin, E.; Lo¨nn, H.; Norberg, T. J . Carbohydr. Chem.
1989, 8, 597.
(8) Shibata, S.; Nakanishi, H. Carbohydr. Res. 1980, 86, 316.
(9) Attard, G. S.; Balckaby, W. P.; Leach, A. R. Chem. Phys. Lipids
1994, 74, 83.
(10) (a) Cerezo, A. S. Chem. Ind. 1971, 96. (b) Cerezo, A. S. Ann.
Asoc. Quim. Argent. 1976, 64, 351.
(11) Schmidt, R. R.; Klotz, W. Synlett 1991, 169.

610 J . Org. Chem., Vol. 63, No. 3, 1998
Retailleau et al.
F igu r e 1. 13C NMR Spectra (75 MHz) of 1a (top) and 2a (bottom) in DMSO-d6, from 60 to 175 ppm.
a
Ta ble 2. 1H NMR (300 MHz) Da ta of Com p ou n d 1a in DMSO-d 6
1a B
) 7.4 Hz
1a A
) 8.7 Hz
1-H2
3
3
H1
H2
H3
4.76 ppm, d, J H
3.27 ppm
3.24 ppm
5.38 ppm, d, J H
3.22 ppm
3.16 ppm
1-H2
H4
H5
H6a
H6b
H8
H9cis
H9trans
H10
H11
OH2
OH3
OH4
OH6
3.09 ppm
3.25 ppm
3
2
3.40 ppm, ddd, J ) 2.2, 5.5 Hz, J ) 11.9 Hz
3
2
3.66 ppm, ddd, J ) 6.0, 5.5 Hz, J ) 11.9 Hz
3
6.69 ppm, dd, J ) 17, 11 Hz
3
2
3
2
5.75 ppm, dd, J ) 11 Hz, J ) 2.5 Hz
5.65 ppm, dd, J ) 11 Hz, J ) 2.5 Hz
3 2
3
2
6.20 ppm, dd, J ) 17 Hz, J ) 2.5 Hz
6.08 ppm, dd, J ) 17 Hz, J ) 2.5 Hz
3.25 ppm (broad)
1.52 ppm (broad)
3
3
5.20 ppm, d, J ) 5 Hz
5.13 ppm, d, J ) 4 Hz
4.98 ppm, db, J ) 5 Hz
5.09 ppm, d, J ) 4 Hz
3
3
3
5.03 ppm, d, J ) 5 Hz
3
4.48 ppm, tb, J ) 5.6 Hz
a
Assignments made from 2D 13C-1H, 1H-1H (COSY), J -resolved spectra. The atoms are numbered as shown in Scheme 2 and Figure
3.
1
The H and 13C NMR spectra of compounds 1a -f in
1H-1H (COSY) NMR spectra; the coupling constants
have been determined from a 1H-1H J -resolved spec-
trum. The spectroscopic data and spectra of compound
1a are used to illustrate the following structural discus-
sion.
DMSO-d6 are more complicated since they exhibit a
doubling of some resonances, mainly for the glucose ring
and the acryloyl substituent, with a relative intensity 70/
30 indicating the presence of two species 1A (∼30%) and
1B (∼70%) in solution whatever the alkyl chain length
1
The 13C and H NMR data of the major species 1B are
1
(Tables 1 and 2, Figures 1 and 2). This doubling of H
close to those of compounds 2. The 13C signals of species
1A only slightly differ from 1B for the glucose nuclei and
the acryloyl substituent (∆δ ≈ 0.1-1.5 ppm), the main
difference being observed for C1 nuclei (86.4 ppm for 1a B
and 82.2 ppm for 1a A, Figures 1 and 2, Table 1). The
1H NMR spectra of compounds 1 show two sets of signals
for terminal ethylenic protons H9A and H9B and two well-
separated resonances for H1A and H1B nuclei: the H1B
chemical shift is very close to those observed for com-
pounds 2 (4.76 ppm for 1a B and 4.68 ppm for 2a ,
and 13C resonances demonstrates the existence of two
rotational isomers 1A and 1B in solution. Spectral
assignments have been performed using 2D 13C-1H and
(12) (a) Montaudo, G.; Librando, V.; Caccamese, S.; Maravigna, P.
J . Am. Chem. Soc. 1973, 95, 6365. (b) Montaudo, G.; Maravigna, P.;
Caccamese, S.; Librando, V. J . Org. Chem. 1974, 39, 2806. (c)
Montaudo, G.; Caccamese, S.; Librando, V.; Maravigna, P. Tetrahedron
1973, 29, 3915. (d) Szalontai, G.; Sandor, P.; Bangerter, F.; Kollar, L.
Magn. Reson. Chem. 1989, 27, 216. (e) Hobson, R. F.; Reeves, L. W. J .
Magn. Reson. 1973, 10, 243.

New Reactive Sugar Surfactants
J . Org. Chem., Vol. 63, No. 3, 1998 611
but without structural assignments.9,14 N-alkyl-N-acryl-
oylglucosylamines 1a -f behave like other N,N-dialkyl-
substituted tertiary amides, including disubstituted acryl-
amides,15 for which the ratio of the two rotamers usually
depends on steric repulsions between the substituents
and favors the conformation where the bulkiest substitu-
ent is cis to the carbonyl oxygen atom.13,15,16 Accordingly,
for compounds 1a -f, the exo (A)-endo (B) rotamer ratio
is almost constant (∼30/70) whatever the alkyl chain
length.
On the other hand, for N-alkylglucosylmethacryl-
amides 2, steric repulsions between the methyl group on
C8 and the glucose ring destabilize the exo rotamer so
that the endo rotamer is the sole rotational isomer
observed in solution in DMSO as well as in other usual
solvents including protic solvents such as methanol
and water. Such an effect of the steric hindrance of the
CdO substituent has been described for other tertiary
amides.13,16a
3. Stu d y of th e En d o-Exo Isom er Equ ilibr iu m
of N-Alk ylglu cosyla cr yla m id es 1a -f. 3.1. NOESY.
The NOESY spectrum of N-octylglucosylacrylamide (1a )
in DMSO-d6 (Figure 4) clearly shows correlation peaks
between the anomeric protons H1A and H1B and between
the ethylenic protons H9A (cis and trans) and H9B (cis
and trans) of the two rotamers A and B, thereby sup-
porting a conformational equilibrium between the exo (A)
and endo (B) rotamers.17
The NOESY spectrum also demonstrates the spatial
proximity of the ethylenic H8 nuclei with the anomeric
proton H1A or H1B. Molecular models show indeed that
H8 and H1 are close together in the exo rotamer A, with
a minimal interatomic distance of about 1.9 Å, for an s-cis
conformation of the acryloyl group. In addition, the
absence of a correlation peak between H9A(trans) and
H1A is also in agreement with an s-cis conformation of
the acryloyl group (approximative minimal distances H9-
A(trans)-H1A: about 1 and 4.5 Å, respectively, for s-trans
and s-cis conformations of the acryloyl group). For the
endo rotamer B, molecular models indicate that (i)
whatever the conformation s-cis or s-trans of the acryloyl
group, spatial interactions between the ethylenic protons
(H9B trans and cis) and the anomeric proton H1B are not
expected, and (ii) the ethylenic protons H9B trans and
the protons H10 and H11 of the alkyl chain are close
together for a s-trans conformation of the acryloyl group
(approximative minimal distances H9B(trans)-H10 and
F igu r e 2. 2D Heteronuclear 13C-1H NMR Spectrum of 1a in
DMSO-d6 a (bottom): Ethylenic region (125 to 130 ppm - 5.5
to 6.9 ppm) b (top): Glucose region (55 to 90 ppm - 3.0 to 5.5
ppm)
respectively, Figure 2, Table 2). On the other hand, the
H1 nucleus of species 1A is deshielded (5.38 ppm): the
characteristic trans coupling constant with H2 (8.7 Hz)
confirms the â-structure of species 1A. Molecular model-
ing shows that in the exo rotamer (with the glucose ring
anti to the carbonyl oxygen atom, Scheme 2) the anomeric
proton H1 and the carbonyl group are close together (∼2.7
Å) and that H1 lies in the deshielding area of the
carbonyl, in agreement with the high value of the
observed low-field resonance of H1A (Figure 3). The
deshielding of proton nuclei trans to the oxygen atom is
indeed well-known for N-methylamides.13
H9B(trans)-H11
: 1.3-2 Å) and far away for a s-cis
conformation of the acryloyl group. The absence of
correlation peaks with the alkyl-chain nuclei clearly
demonstrates an s-cis conformation. Thus, the acryloyl
group adopts an s-cis conformation in both the endo (B)
and the exo (A) rotamers of N-alkyl-N-acryloylglucosyl-
(14) (a) Lockhoff, O. Angew. Chem., Int. Ed. Engl. 1991, 30, 1611.
(b) Vigdorchik, M. M.; Kostyuchenko, N. P.; Okad’ko, G. S.; Sheinker,
Y. N.; Suborov, N. N. J . Org. Chem. USSR (Engl. Trans.) 1973, 9, 617.
(15) De Riggi, I.; Gastaldi, S.; Surzur, J . M.; Bertrand, M. P. J . Org.
Chem. 1992, 57, 6118.
Therefore, N-alkylglucosylacrylamides 1 exist in DMSO
solution as two rotamers in equilibrium: an exo isomer
1A and an endo isomer 1B (Scheme 2). The existence of
two rotamers has already been observed for other tertiary
glucosylamides such as N-alkyl-N-alkanoylglucosylamines
(16) Robin, M. B.; Bovey, F. A.; Basch, H. In The Chemistry of
Amides; Pata¨ı, S., Zabicky, J ., Eds.; J ohn Wiley & Sons: New York,
1970; p 1. (b) Challis, B. C.; Challis, J . A. In Comprehensive Organic
Chemistry; Barton, D. H. R., Ollis, W. D., Eds.; Pergamon Press: New
York, 1979; Vol. 2, p 958. (c) Laplanche, L. A.; Rogers, M. T. J . Am.
Chem. Soc. 1963, 85, 3728.
(17) (a) Perrin, C. L.; Dwyer, T. J . Chem. Rev. 1990, 90, 935. (b)
Grozinger, K. J .; Kriwacki, R. W.; Leonard, S. E.; Pitner, T. P. J . Org.
Chem. 1993, 58, 712.
(13) Stewart, W. E.; Siddal, T. H. Chem. Rev. 1970, 70, 517.

612 J . Org. Chem., Vol. 63, No. 3, 1998
Retailleau et al.
F igu r e 3. Molecular models of both endo and exo rotamers of N-(â-D-glucopyranosyl)-N-octyl-acrylamide 1a.
Sch em e 3
amines 1. The preferred s-cis conformation of acryl-
amides is well-documented.12
3.2. In flu en ce of th e Solven t: Evid en ce for In -
tr a m olecu la r Hyd r ogen Bon d in g in th e En d o Iso-
m er B. 1H and 13C NMR spectra of compounds 1a -f
recorded in various solvents such as pyridine, DMSO, and
methanol show that the exo/endo (A/B) isomer ratio
remains almost constant (from 25/75 to 35/65). Temper-
ature-dependent 1H NMR spectra of compound 1a in
deuterated methanol show that the exo/endo (A/B) ratio
is only slightly increased from 30/70 to 40/60 when the
temperature is lowered from +35 to -40 °C and remains
almost constant (30/70) above 0 °C. Unfortunately,
experiments cannot be performed at higher temperatures
since polymerization occurs above 40-50 °C.
On the other hand, in water, the exo/endo (A/B) ratio
increases to 50/50, demonstrating that the amount of
endo isomer is significantly decreased in protic medium.
The A/B ratio in water is not concentration-dependent
and remains almost constant below and above the critical
micelle concentration (vide infra), thus indicating that
micellization does not shift the exo-endo equilibrium.
Moreover, the addition of 2 equiv of trifluoroacetic acid
to 1a in D2O gives rise to a significant increase of the
exo/endo ratio (A/B) from 50/50 in pure water to 80/20 in
the presence of acid (Figure 5).
sible for the increased stability of the endo rotamer B in
polar aprotic and poorly protic solvents.
To further check this hypothesis, the tetra-O-acetylated
compounds 4a and 4f have been synthesized (Scheme 3)
and characterized by 1D and 2D homo and heteronuclear
NMR spectroscopy. The 1H and 13C NMR spectra of
acetylated compounds 4a and 4f show for both deriva-
tives the presence of the exo (A) and endo (B) rotamers,
easily identified by their anomeric protons (H1A and H1B,
respectively, at 5.95 and 5.53 ppm in CD3OD for 4a ), with
an exo/endo isomer ratio of 50/50 in methanol and 70/30
in chloroform. Therefore, when hydrogen bonding cannot
take place, the exo/endo equilibrium is shifted toward the
exo isomer (A) even with a much bulkier tetra-O-
acetylglucopyranosyl substituent.
An intramolecular hydrogen bond may thus account
for the predominance of the sterically unfavored endo (B)
rotamer for N-alkylglucosylacrylamides 1a -f in polar
aprotic and poorly protic solvents.18
This variation of the exo/endo (A/B) ratio, leading to
the predominance of the exo (A) rotamer in protic acidic
medium, can be explained by the existence of a strong
intramolecular hydrogen bond in the endo (B) rotamer,
between the glucopyranosyl hydroxyl group OH2 and the
oxygen of the amide group, in polar aprotic and poorly
protic solvents. The splitting of the OH2 resonance in
DMSO (4.98 and 5.20 ppm, respectively, for OH2A and
OH2B) and the higher chemical shift for the endo rotamer
(B) confirm this assumption. Furthermore, molecular
models of the endo (B) rotamer show that the oxygen of
the carbonyl group is very close to the hydroxyl substitu-
ent of the glucose carbon C2 (approximative minimal
distance OH2/OdC ≈ 0.7 Å, Figure 3). This intramo-
lecular hydrogen bond between the carbonyl group and
the hydroxyl substituent OH2 may thus well be respon-
4. Su r fa cta n t P r op er ties. N-Alkylglucosyl(meth)-
acrylamides 1 and 2 are fairly soluble in water for alkyl
chain lengths up to 14 carbon atoms; the octadecyl
derivative 1e is the only water-insoluble compound.
Moreover, surprisingly, the solubility in water does not
vary significantly with the alkyl chain length: about 3
× 10-2 mol/L for the octyl derivative 1a and 1 × 10-2
mol/L for the tetradecyl derivative 1d . It is noteworthy
that our glucosyl(meth)acrylamides 1 and 2 are much
more water-soluble than classical alkyl glucosides and
thioglucosides.19,20
(18) (a) Sagar, B. F. J . Chem. Soc. B 1967, 428. (b) Marcovici-
Mizrahi, D.; Gottlieb, H. E.; Marks, V.; Nudelman, A. J . Org. Chem.
1996, 61, 8402.
(19) Shinoda, K.; Yamaguchi, T.; Hori, R. Bull. Chem. Soc. J pn.
1961, 34, 237.

New Reactive Sugar Surfactants
J . Org. Chem., Vol. 63, No. 3, 1998 613
F igu r e 4. NOESY Spectrum (DMSO-d6, 300 MHz, mixing time: 0.9s) of 1a, from 4.4 to 6.8 ppm.
Surface tension measurements of aqueous solutions at
25 °C demonstrate that N-alkylglucosyl(meth)acryl-
amides 1a -d and 2a ,d are surfactants (Figure 6). The
parameters derived from these measurements are given
in Table 3. On the other hand, for the butylphenyl
derivative 1f, no micelle formation could be observed up
to its solubility limit (5 × 10-2 mol/L). It behaves rather
like a hydrotrope owing to the polarity of the aromatic
nucleus.21
The critical micelle concentrations (cmc) of compounds
1a -d and 2a ,d decrease with the alkyl chain length.
Log(cmc) displays a linear dependence on the number of
(20) Saito, S.; Tsuchiya, T. Chem. Pharm. Bull. 1985, 33(2), 503.

614 J . Org. Chem., Vol. 63, No. 3, 1998
Ta ble 3. Va lu es Obta in ed fr om Su r fa ce Ten sion Mea su r em en ts for Com p ou n d s 1 a n d 2a
Retailleau et al.
cmc (mol/L)
Γ (mmol/m2)
as (Å2)
γ
cmc (mN/m)
1a
1b
1c
1d
2a
2d
R ) C8H17
R ) C10H21
R ) C12H25
R ) C14H29
R ) C8H17
R ) C14H29
(1.2 ( 0.2) × 10-2
(1.2 ( 0.1) × 10-3
(1.4 ( 0.1) × 10-4
(3.0 ( 0.1) × 10-5
(8.0 ( 0.5) × 10-3
(1.7 ( 0.3) × 10-5
2.5 ( 0.2
3.1 ( 0.1
3.5 ( 0.1
4.2 ( 0.2
2.7 ( 0.5
4.4 ( 0.5
67 ( 4
53 ( 2
47 ( 2
39 ( 3
60 ( 5
38 ( 4
35.5
33.5
32.2
31.8
34.0
33.5
alkylglucosides19
R ) C8H17
R ) C10H21
R ) C12H25
2.5 × 10-2 (1.9 × 10-2
)
3.9
3.5
4.6
42 (43)c
47 (43)c
36
30.1
27.7
39.4
b
2.2 × 10-3
1.9 × 10-4
a
The superficial excess Γ and the area per headgroup as are calculated below the cmc from the Gibbs adsorption isotherm: dγ )
-ΓRTdLnC. γcmc is the superficial tension above the cmc. From ref 22. c From ref 24.
b
F igu r e 6. Air-water interfacial tension γ vs concentration
for surfactants 1a-d at 25 °C.
F igu r e 5. 1H NMR Spectra (300 MHz) of 1a, from 4.7 to 6.9
ppm a (bottom): in D2O b (top): in D2O + 2eq.TFA
carbon atoms in the aliphatic chain nc. It follows the
Klevens equation, log(cmc) ) a - bnC, as with classical
nonionic surfactants such as alkylglucosides19 and alkyl-
thioglucosides20 (Figure 7). Nevertheless, the smaller
values of the intercept and gradient obtained for com-
pounds 1 and 2 as well as the lower cmc values of
compounds 1a -c and 2a compared to the homologous
alkylglucosides19,22 may be due to a weak contribution of
the (meth)acryloyl substituent to the free energy of
micellization. Furthermore, the lower cmc of methacryl-
oyl compounds 2a and 2d compared to their acryloyl
homologs 1a and 1d clearly indicates that the methyl
group has a hydrophobic contribution.
F igu r e 7. log cmc (mol/L) versus number of carbon atoms nC
of the alkyl substituent. 1a -d : log(cmc 1) ≈ 1.51 - 0.44nC;
2a ,d : log(cmc 2) ≈ 1.45 - 0.45nC; alkylglucosides:19 log(cmc)
≈ 2.64 - 0.53nC.
tion of the (meth)acryloyl group at the interface23 may
account for the high values of as for compounds 1a -c and
2a compared to those reported for alkyl glucosides.19,24
Con clu sion
N-Alkylglucosyl(meth)acrylamides, new polymerizable
and Michael acceptor surfactants, are conveniently pre-
pared in two steps from glucose. The structural analysis
demonstrates the existence of a rotational isomerism that
is strongly dependent on the steric hindrance of the
unsaturated substituent: both endo and exo isomers are
observed for the acrylamido derivatives while the endo
The area per headgroup as for compounds 1a -d and
2a ,d , evaluated using the Gibbs adsorption isotherm,
ranges from 67 to 38 Å2. It decreases when the alkyl
chain length is increased, probably because of increasing
chain-chain interactions in the monolayer.25 The loca-
(21) Larpent, C.; Bernard, E.; Brisse-LeMenn, F.; Patin, H. J . Mol.
Catal. A 1997, 116, 277.
(22) Focher, B.; Savelli, G.; Torri, G.; Vecchio, G.; McKenzie, D. C.;
Nicoli, D. F.; Bunton, C. A. Chem. Phys. Lett. 1989, 158, 491.
(23) Hamid, S. M.; Sherrington, D. C. Polymer 1987, 28, 325.
(24) Puvvada, S.; Blankschtein, D. J . Chem. Phys. 1990, 92, 3710.
(25) Eastoe, J .; Rogueda, P.; Howe, A. M.; Pritt, A. R.; Heenan, R.
K. Langmuir 1996, 12, 2701.

New Reactive Sugar Surfactants
J . Org. Chem., Vol. 63, No. 3, 1998 615
13C NMR (DMSO-d6) δ 13.19 (CH3), 22.09, 26.85, 28.73, 29.10,
29.96 and 31.30 (CH2 alkyl), 45.55 (NCH2), 61.13 and 61.36
(C6R and â), 70.50, 70.65, 70.90, 71.57, 73.47, 73.71, 77.40 and
77.56 (C2, C3, C4, C5, R and â), 86.91 (C1R), 90.76 (C1â).
Isomeric ratio: R/â ) 20/80. 3c: 60% yield; mp 106 °C (lit.4
mp 105.5 °C); H NMR (DMSO-d6) δ 0.84 (t, 3H, CH3, J ) 7
Hz), 1.23 (m, 18H, CH2 alkyl), 1.37 (b, 2H, NCH2CH2), 2.17
(b, 1H, NH), 2.48 (mb, 1H, NCH2), 2.81 (mb, 1H, H2), 3.00 (m,
2H, H4, H5), 3.10 (m, 1H, H3), 3.39 (m, 1H, H6a), 3.55 (m, 1H,
rotamer is the sole species observed in the case of
N-alkylglucosylmethacrylamides. The influence of the
protic medium on the N-alkylglucosylacrylamides endo-
exo equilibrium and the comparison with their acetylated
derivatives suggest that an intramolecular hydrogen
bond may be responsible for the increased stability of the
endo rotamer. The surfactant properties of N-octyl- to
-tetradecyl-substituted glucosyl(meth)acrylamides are
similar to usual sugar-based surfactants. Furthermore,
their fairly high solubility in water suggests that they
may have valuable biological applications.20 The syn-
thetic applications of these new reactive sugar-based
surfactants 1a -d and 2a ,d for the preparation of func-
tionalized, chiral surfactants are currently being studied.
1
3
H
6b), 3.62 (d, 1Hâ, H1â, 3J H
) 7 Hz), 4.28 (b, 1HR, H1R),
-H
1
2
4.33 (t, 1H, OH6, 3J ) 6 Hz), 4.44 (d, 1H, OH2, 3J ) 4 Hz),
3
3
4.79 (d, 1H, OH3, J ) 3 Hz), 4.83 (d, 1H, OH4, J ) 4.5 Hz);
13C NMR (DMSO-d6) δ 13.91 (CH3), 22.11, 26.87, 28.73, 29.03,
29.09, 29.11, 29.59, 29.98, and 31.31 (CH2 alkyl), 45.48 and
45.92 (NCH2 R and â), 61.37 (C6), 70.65 and 70.93 (C4 R and
â), 73.49 and 73.72 (C2 R and â), 77.43 (C5), 77.59 (C3), 86.92
(C1R), 90.79 (C1â). Isomeric ratio: R/â ) 20/80. 3d : 78% yield;
mp 107-109 °C; 1H NMR (DMSO-d6) δ 0.84 (t, 3H, CH3, J )
3
Exp er im en ta l Section
7 Hz), 1.23 (m, 10H, CH2 alkyl), 1.38 (b, 2H, NCH2CH2), 2.50
(mb, 1H, NCH2), 2.82 (mb, 1H, H2), 3.02 (m, 2H, H4, H5), 3.12
(m, 1H, H3), 3.34 (m, 1H, H6a), 3.58 (m, 1H, H6b), 3.63 (d, 1Hâ,
Gen er a l Meth od s. All unspecified reagents were from
commercial resources. The IR spectra were recorded using a
FTIR apparatus. The NMR spectra were obtained on a Bruker
AM300 spectrometer, 1H (300 MHz) and 13C (75.5 MHz). Mass
spectra in the chemical ionization mode (CI, reactant gas NH3)
were obtained by direct introduction; for electrospray the
samples were diluted in CH3CN/HCO2H 1% in water (50/50).
Elemental analyses have been obtained from the “Service
Central d’Analyse” (CNRS, Vernaison, France). HPLC analy-
ses were carried out in both the normal mode [method A, silica
3
3
H1â, J H
) 8 Hz), 4.30 (b, 1HR, H1R), 4.33 (t, 1H, OH6, J
-H
1
2
3
) 6 Hz), 4.46 (d, 1H, OH2, J ) 4 Hz), 4.81 (b, 1H, OH3), 4.84
(d, 1H, OH4, 3J ) 4.5 Hz); 13C NMR (DMSO-d6) δ 13.96 (CH3),
22.08, 26.85, 28.70, 29.00, 29.05, 29.08, 29.57, 29.98, and 31.28
(CH2 alkyl), 45.55 and 45.91 (NCH2 R and â), 61.37 (C6), 70.67
and 70.95 (C4 R and â), 73.51 and 73.71 (C2 R and â), 77.44
(C5), 77.61 (C3), 86.91 (C1R), 90.79 (C1â). Isomeric ratio: R/â
) 20/80. 3e: 78% yield; mp 104 °C (lit.4 103.5 °C); 13C NMR
(C5D5N, 22.5 MHz) δ 14.31 (CH3), 22.95 (CH2 alkyl), 27.75 (CH2
alkyl), 29.67 (CH2 alkyl), 30.02 (CH2 alkyl), 31.02 (CH2 alkyl),
32.19 (CH2 alkyl), 46.63 (CH2N, â), 47.12 (CH2N, R), 62.96 (C6
â), 63.18 (C6 R), 71.90 (C4 â), 72.52 (C4 R), 75.01 (C2 â), 75.66
(C2 R), 79.02 (C3, C5), 88.50 (C1 R), 92.05 (C1 â). Isomeric
ratio: R/â ) 20/80. 3f: 41% yield; mp 64-66 °C; IR (KBr, ν
cm-1) 3420, 3325, and 3257 (OH, NH), 3026, 2999, 2950-2830,
column (15 cm), eluent: methanol/water 80/20, 1.5 mL‚min-1
,
UV detection 235 nm] and the reverse mode [method B, RP18
column (15 cm), eluent: dichloromethane/methanol 96/4, 2
mL‚min-1, UV detection 230 nm]. Capacity factor: k′ ) (tr -
t0)/t0. TLC on silica plates (Merck 60F254); indicators: I, UV
254 nm; II, sulfuric acid (20% in ethanol); III, ninhydrine (0.2%
in ethanol). Molecular models were obtained using CS Chem3D
software, MM2-minimized energy. Surface tension was mea-
sured using a Kru¨ss K10 tensiometer and Pt du Nouy ring,
thermostated at 25 °C. The aqueous solutions were prepared
using ultrapure water (MilliQ, resistivity > 18 MΩ) and
previously freeze-dried compounds. The concentration of
residual ions, measured by capillary electrophoresis, was
always very low (<0.05 mol per mol surfactant).
1
1650 and 1500 (νCdC); H NMR (DMSO-d6) δ 1.45-1.38 (m,
2H, NCH2CH2), 1.64-1.54 (m, 2H, CH2CH2Ph), 2.18 (bp, 1H,
N-H), 2.59-2.53 (m, 3H, NCHa and CH2Ph), 2.89-2.77 (m,
2H, H2, and NCHb), 3.00 (m, 2H, H4, H5), 3.13-3.08 (m, 1H,
H3), 3.42-3.38 (m, 1H, H6b), 3.67-3.62 (m, 2H, H1â, H6a), 4.30
(d, 1HR, H1R, J ) 5.5 Hz), 4.36 (dd, 1H, OH6, J ) 5.5, 5.9 Hz),
4.45 (d, 1H, OH2, J ) 4.0 Hz), 4.80 (d, 1H, OH4, J ) 4.4 Hz),
4.83 (d, 1H, OH3, J ) 4.8 Hz), 7.25-7.13 (m, 5H, ArH); 13C
NMR (DMSO-d6) δ 28.96 (NCH2CH2 or CH2CH2Ph, â), 28.07
and 29.38 (NCH2CH2 and CH2CH2Ph, R), 29.79 (NCH2CH2 or
CH2CH2Ph, â), 35.26 (CH2Ph, R), 35.32 (CH2Ph, â), 45.53
(NCH2, â), 45.89 (NCH2, R), 61.39 (C6R), 61.63 (C6â), 70.94,
71.23, 71.83, and 73.72 (C2R, C3R, C4R, C5R), 70.75, 73.94, 77.66
and 77.82 (C2â, C3â, C4â, C5â), 87.13 (C1R), 90.98 (C1â), 125.75,
128.40 and 128.49 (CAr), 142.52 (Cipso). Isomeric ratio: R/â )
20/80. Anal. Calcd for C16H25O5N‚H2O: C, 58.34; H, 8.26; N,
4.25. Found: C, 58.48; H, 8.67; N, 4.31.
N-Alk yl-D-glu cop yr a n osyla m in es 3a -f. N-Octyl-D-glu-
copyranosylamine (3a ), N-decyl-D-glucopyranosylamine (3b),
N-dodecyl-D-glucopyranosylamine (3c), N-tetradecyl-D-glucopy-
ranosylamine (3d ), N-octadecyl-D-glucopyranosylamine (3e),
and N-butyl-4-phenyl-D-glucopyranosylamine (3f) were pre-
pared by reaction of D-glucose with the corresponding alkyl-
amine (stoichiometric amount) in methanol at 60-65 °C,
according to the previously described procedures.4 3a , 3b, 3c,
3d , and 3e were purified by repeated recrystallization in
absolute ethanol until the melting point remained constant
(usually three recrystallizations). 3f was recrystallized twice
from EtOH/H2O (9/1).
N-(â-D-Glu cop yr a n osyl)-N-octyla cr yla m id e (1a ). So-
dium carbonate (6.63 g, 62.5 mmol) was added to a solution of
3a (7 g, 24 mmol) in 100 mL of methanol containing 100 ppm
of sodium nitrite (radical inhibitor). The resulting mixture
was cooled to 0 °C with an ice bath, and 3.9 mL (48 mmol) of
acryloyl chloride was added dropwise via a dropping funnel
in 5 min. The ice bath was then removed. The reaction
mixture was stirred for 25 min at room temperature (TLC
analysis) and then poured into 100 mL of water. After removal
of methanol under reduced pressure, the crude product was
extracted with ethyl acetate (6 × 50 mL). The combined
organic phases were washed with a saturated solution of
sodium bicarbonate (3 × 50 mL) and brine (3 × 50 mL), dried
over magnesium sulfate, and concentrated under vacuum
(about 100 ppm of di-tert-butylphenol was added before
concentration). Crude 1a (8 g, 95%) as a viscous oil was thus
obtained. 1a was purified by column chromatography on silica
gel using an elution gradient starting with dichloromethane
followed by dichloromethane-methanol 90/10. A second col-
umn, using the same eluent system, was almost always
3a: 86% yield; mp 104-106 °C (lit.4 mp 102 °C); MS
(electrospray) m/z 292 (100, MH+); 1H NMR (DMSO-d6) δ 0.86
3
(t, 3H, CH3, J ) 7 Hz), 1.25 (m, 10H, CH2 alkyl), 1.38 (b, 2H,
NCH2CH2), 2.13 (b, 1H, NH), 2.5 (mb, 1H, NCHa), 2.75 (mb,
1H, NCHb), 2.85 (m, 1H, H2), 3.01 (m, 2H, H4, H5), 3.11 (m,
1H, H3), 3.39 (m, 1H, H6a), 3.62 (m, 1H, H6b), 3.66 (d, 1Hâ,
3
3
H1â, J H
) 7 Hz), 4.29 (d, 1HR, H1R, J H
) 5 Hz), 4.35
-H
-H
1
2
1
2
3
3
(t, 1H, OH6, J ) 6 Hz), 4.45 (d, 1H, OH2, J ) 4 Hz), 4.80 (d,
1H, OH3, 3J ) 4.5 Hz), 4.84 (d, 1H, OH4, 3J ) 4.5 Hz); 13C
NMR (DMSO-d6) δ 13.90 (CH3), 22.03, 26.78, 28.67, 28.96,
29.90 and 31.21 (CH2 alkyl), 45.48 (NCH2), 61.31 (C6), 70.46
(C4), 73.44 (C2), 77.37 (C5), 77.55 (C3), 86.92 (C1R), 90.72 (C1â).
Isomeric ratio: R/â ) 20/80. 3b: 65% yield; mp 103 °C (lit.4
mp 103-104 °C); 1H NMR (DMSO-d6) δ 0.84 (t, 3H, CH3, 3J )
7 Hz), 1.24 (m, 14H, CH2 alkyl), 1.35 (b, 2H, NCH2CH2), 2.16
(b, 1H, NH), 2.49 (mb, 1H, NCH2), 2.82 (mb, 1H, H2), 3.00 (m,
2H, H4, H5), 3.10 (m, 1H, H3), 3.37 (m, 1H, H6a), 3.62 (m,
3
1H,H6b), 3.65 (d, 1Hâ, H1â, J H
) 7 Hz), 4.3 (b, 1HR, H1R),
-H
1
2
4.35 (t, 1H, OH6, 3J ) 6 Hz), 4.44 (d, 1H, OH2, 3J ) 4 Hz),
4.79 (d, 1H, OH3, J ) 3 Hz), 4.83 (d, 1H, OH4, J ) 4.5 Hz);
necessary in order to obtain
a product free of impurity
3
3
according to the TLC analysis: yield of purification 52%

616 J . Org. Chem., Vol. 63, No. 3, 1998
Retailleau et al.
(amorphous paste); TLC Rf ) 0.22 (CH2Cl2/MeOH, 9/1); HPLC
31.25 (CH2 alkylB), 41.00 (b, C10A), 42.26 (C10B), 61.06 (C6B),
61.17 (C6A), 69.81 (C4B), 69.91 (C2A), 70.02 (C4A), 70.43 (C2B),
77.49 (C5B), 77.69 (C5A), 78.99 (C3B), 79.33 (C3A), 82.17 (C1A),
86.40 (C1B), 126.58 (C9B), 128.10 (C9A), 128.99 (C8A), 129.70
(C8B), 166.08 (C7A), 166.74 (C7B). Anal. Calcd for C21H39-
NO6‚0.3H2O: C, 62.01; H, 9.74; N, 3.44; O, 24.80. Found: C,
61.95; H, 9.85; N, 3.41; O, 24.83.
(method B) k′ ) 0.9; [R]20 ) +16.7 (c ) 1.5, EtOAc); MS (CI,
D
NH3) m/z 346 (100, MH+); IR (Nujol, ν cm-1) 3500-3200 (OH),
1
1650 (CO, amide I), 1610 (CdC); H NMR (DMSO-d6) δ 0.86
(t, 3H, CH3, 3J ) 7 Hz), 1.25 (m, 10H, H12-16), 1.52 (b, 2H,
H
11), 3.09 (m, 1H, H4), 3.16 (m, 1HA, H3), 3.21 (m, 1HA, H2),
3.24 (m, 1HB, H3), 3.25 (m, 1H, H5), 3.25 (mb, 2H, H10), 3.28
3
3
2
(m, 1HB, H2), 3.40 (ddd, 1H, H6a, J ) 2.2 Hz, J ) 5.5 Hz, J
N-(â-D-Glu cop yr a n osyl)-N-tetr a d ecyla cr yla m id e (1d )
was prepared using a modified procedure owing to the low
solubility of 3d in methanol. Typical procedure: 6.4 g (17
mmol) of 3d was solubilized in 200 mL of THF at 50-60 °C.
Sodium carbonate (27 g, 25.5 mmol) in 40 mL of water, 100
mg of sodium nitrite, and 40 mL of methanol were then added.
The resulting mixture was cooled to 0 °C with an ice bath,
and 9 mL (111 mmol) of acryloyl chloride was then added
dropwise via a dropping funnel in 15 min. The reaction and
treatment were then carried out using the procedure described
above for 1a : reaction time 2 h; quantitative yield of crude
1d , viscous oil; yield of purification (elution gradient CH2Cl2/
MeOH) 60% (amorphous paste); TLC Rf ) 0.22 (CH2Cl2/MeOH,
) 11.9 Hz), 3.66 (ddd, 1H, H6b, 3J ) 6.0, 5.5 Hz, 2J ) 11.9 Hz),
4.48 (m, 1H, OH6), 4.76 (d, 1HB, H1B, J H
3
) 7.4 Hz), 4.98
-H
1
2
3
3
(d, 1HA, OH2A, J ) 5 Hz), 5.03 (d, 1H, OH4, J ) 5 Hz), 5.09
3
3
(d, 1HA, OH3A, J ) 4 Hz), 5.13 (d, 1HB, OH3B, J ) 4 Hz),
3
3
5.20 (d, 1HB, OH2B, J ) 5 Hz), 5.38 (d, 1HA, H1A, J H
)
-H
1
2
3
2
8.7 Hz), 5.65 (dd, 1HB, H9cisB, J ) 11 Hz, J ) 2.5 Hz), 5.75
(dd, 1HA, H9cisA, 3J ) 11 Hz, 2J ) 2.5 Hz), 6.08 (dd, 1HB,
3
2
3
H
9transB, J ) 17 Hz, J ) 2.5 Hz), 6.20 (dd, 1HA, H9transA, J
2 3
) 17 Hz, J ) 2.5 Hz), 6.69 (dd, 1H, H8, J ) 17, 11 Hz); the
exo (A)-endo (B) isomer ratio 27/73 was calculated from the
integration curve of protons H9cisA/H9cisB, H9transA/H9transB, and
H1A/H1B; 13C NMR (DMSO-d6) δ 13.90 (CH3), 22.03 (CH2
alkyl), 26.40 (CH2 alkyl), 26.71 (CH2 alkyl), 28.39 (C12B), 28.62
(CH2 alkyl), 28.71 (CH2 alkyl), 30.70 (C12A), 31.21 (CH2 alkyl),
42.26 (C10), 61.06 (C6B), 61.17 (C6A), 69.80 (C4B), 69.91 (C2A),
70.00 (C4A), 70.43 (C2B), 77.49 (C5B), 77.67 (C5A), 78.97 (C3B),
79.31 (C3A), 82.17 (C1A), 86.39 (C1B), 126.59 (C9B), 128.14
(C9A), 128.98 (C8A), 129.68 (C8B), 166.09 (C7A), 166.76 (C7B).
Anal. Calcd for C17H31NO6‚0.5H2O: C, 57.63; H, 9.04; N, 3.95;
O, 29.38. Found: C, 57.51; H, 9.12; N, 3.98; O, 29.41.
9/1); HPLC (method B): k′ ) 6.7; [R]20 ) +10.7 (c ) 1.5,
D
CH2Cl2); MS (CI, NH3) m/z 430 (100, MH+); IR (Nujol, ν cm-1
)
1
3500-3200 (OH), 1650 (CO, amide I), 1610 (CdC); H NMR
(DMSO-d6) δ 0.85 (t, 3H, CH3, 3J ) 7 Hz), 1.25 (m, 18H, H12-20),
1.52 (b, 2H, H11), 3.05 (m, 1H, H4), 3.20-3.30 (m, 3H, H2, H3,
2
H5), 3.25 (m, 2H, H10), 3.40 (m, 1H, H6a), 3.66 (db, 1H, H6b, J
) 11 Hz), 4.47 (b, 1H, OH6), 4.76 (d, 1HB, H1B, 3J H
) 7
-H
1
2
Hz), 4.94 (b, OH), 4.99 (b, OH), 5.09 (b, OH), 5.16 (b, OH),
3
3
N-(â-D-Glu cop yr a n osyl)-N-d ecyla cr yla m id e (1b) was
prepared using the procedure described above for 1a : quan-
titative yield of crude 1b, viscous oil; yield of purification
(elution gradient CH2Cl2/MeOH) 70% (amorphous paste); TLC
Rf ) 0.22 (CH2Cl2/MeOH, 9/1); HPLC (method B) k′ ) 1.6);
[R]20D ) +14 (c ) 2, EtOAc); MS (CI, NH3) m/z 374 (100, MH+);
IR (Nujol, ν cm-1) 3500-3200 (OH), 1650 (CO, amide I), 1610
(CdC); 1H NMR (D2O) δ 0.87 (t, 3H, CH3, 3J ) 7 Hz), 1.28 (m,
18H, H12-20), 1.62 (b, 2H, H11), 3.0-3.60 (m, 6H, H2, H3, H4,
5.38 (d, 1HA, H1A, J H
) 8 Hz), 5.64 (dd, 1HB, H9cisB, J
-H
1
2
2
3
) 10.5 Hz, J ) 2 Hz), 5.74 (d, 1HA, H9cisA, J ) 10 Hz), 6.07
(dd, 1HB, H9transB, 3J ) 17 Hz, 2J ) 2 Hz), 6.20 (d, 1HA,
H
9transA, 3J ) 16.5 Hz), 6.68 (dd, 1H, H8, 3J ) 17, 10.5 Hz);
the exo (A)-endo (B) isomer ratio 30/70 is calculated from the
integration curve of protons H9cisA/H9cisB, H9transA/H9transB, and
H1A/H1B; 13C NMR (CD3OD) δ 14.59 (CH3), 23.78, 27.83, 28.15,
28.45, 30.01, 30.35, 30.56, 30.74, 30.81, 30.85, 30.86, 30.88,
30.89, 32.26 and 33.14 (CH2 alkyl), 43.79 (C10B or A), 44.73
(C10A or B), 62.71 (C6A), 62.94 (C6B), 71.22 (C4B), 71.38 (C2A),
71.71 (C4A), 72.09 (C2B), 78.97 (C5B), 79.15 (C5A), 80.32 (C3A),
80.61 (C3B), 84.60 (C1A), 88.55 (C1B), 127.99 (C9A and B),
129.79 (C8A), 130.70 (C8B), 169.88 (C7A), 170.54 (C7B). Anal.
Calcd for C23H43NO6‚0.5H2O: C, 63.01; H, 10.05; N, 3.20; O,
23.74. Found: C, 63.08; H, 10.05; N, 3.28; O, 23.67.
H5, H10), 3.67 (b, 1H, H6a), 3.83 (db, 1H, H6b, J ) 9 Hz), 4.92
3
(b, 1HB, H1B), 5.44 (db, 1HA, H1A, J H
) 8 Hz), 5.76 (db,
-H
1
2
1H, H9cis, J ) 9.5 Hz), 6.11 (d, 1HB, H9transB, 3J ) 17 Hz),
3
3
6.32 (d, 1HA, H9transA, J ) 17 Hz), 6.60 (dd, 1H, H8, J ) 17,
11 Hz); the exo (A)-endo (B) isomer ratio 50/50 was calculated
from the integration curve of protons H9transA/H9transB and H1A/
H1B; 13C NMR (CD3OD) δ 14.47 (CH3), 23.64, 27.98, 28.30,
29.85, 30.37, 30.14, 30.62, 30.69, 32.09 and 32.97 (CH2 alkyl),
43.33 (C10B or A), 44.00 (C10A or B), 62.79 (C6), 71.03 (C4B
and C2A), 71.58 (C4A), 71.95 (C2B), 79.06 (C5), 80.16 (C3), 84.47
(C1A), 88.39 (C1B), 127.91 (C9B), 129.62 (C9A), 129.70 (C8A),
N-(â-D-Glu copyr an osyl)-N-octadecylacr ylam ide (1e) was
prepared using the procedure described above for 1d : yield
of crude 1e 90%; viscous oil; yield of purification (elution
gradient CH2Cl2/MeOH) 55% (white powder); mp 44-45 °C;
TLC Rf ) 0.23 (CH2Cl2/MeOH, 9/1); HPLC (method A) k′) 5.8;
130.50 (C8B), 169.77 (C7A), 170.58 (C7B). Anal. Calcd for C19
35NO6‚0.3H2O: C, 60.25; H, 9.41; N, 3.70; O, 26.64. Found:
C, 60.19; H, 9.56; N, 3.67; O, 26.66.
-
[R]20 ) +7.9 (c ) 1.1, CH2Cl2); MS (CI, NH3) m/z 486 (100,
D
H
MH+); IR (Nujol, ν cm-1) 3500-3200 (OH), 1650 (CO, amide
1
3
I), 1610 (CdC); H NMR (DMSO-d6) δ 0.88 (t, 3H, CH3, J )
7 Hz), 1.25 (m, 18H, H12-20), 1.54 (b, 2H, H11), 3.08 (m, 1H,
H4), 3.20-3.30 (m, 3H, H2, H3, H5), 3.25 (m, 2H, H10), 3.40 (m,
N-(â-D-Glu cop yr a n osyl)-N-d od ecyla cr yla m id e (1c) was
prepared using the procedure described above for 1a : yield of
crude 1c 87%; viscous oil; yield of purification (elution gradient
CH2Cl2/MeOH) 60% (amorphous paste); TLC Rf ) 0.22 (CH2Cl2/
1H, H6a), 3.69 (ddd, 1H, H6b
4.51 (m, 1H, OH6), 4.78 (d, 1HB, H1B, J H
,
3J ) 6.0, 4.5 Hz, 2J ) 11 Hz),
3
) 7.5 Hz), 4.97
-H
1
2
3
MeOH, 9/1); HPLC (method B) k′ ) 3.1; [R]20 ) +13.3 (c )
(b, 1HA, OH2A), 5.03 (d, 1H, OH4, J ) 4.5 Hz), 5.08 (b, 1HA,
D
1.5, EtOAc); MS (CI, NH3) m/z 402 (100, MH+); IR (Nujol, ν
OH3A), 5.13 (b, 1HB, OH3B), 5.20 (d, 1HB, OH2B, 3J ) 4 Hz),
cm-1) 3500-3200 (OH), 1650 (CO, amide I), 1610 (CdC); H
5.40 (d, 1HA, H1A, 3J H 2 ) 8.5 Hz), 5.66 (dd, 1HB, H9cisB, 3J
1
-H
1
2
3
NMR (DMSO-d6) δ 0.86 (t, 3H, CH3, 3J ) 7 Hz), 1.25 (m, 18H,
) 10.5 Hz, J ) 2 Hz), 5.77 (d, 1HA, H9cisA, J ) 10 Hz), 6.10
H
12-20), 1.52 (b, 2H, H11), 3.09 (m, 1H, H4), 3.20-3.30 (m, 3H,
(dd, 1HB, H9transB, 3J ) 17 Hz, 2J ) 2 Hz), 6.22 (d, 1HA,
3
3
H2, H3, H5), 3.25 (m, 2H, H10), 3.40 (m, 1H, H6a), 3.66 (ddd,
H9transA, J ) 17 Hz), 6.71 (dd, 1H, H8, J ) 17, 10.5 Hz); the
3
3
2
1H, H6b, J ) 6.0 Hz, J ) 4.5 Hz, J ) 11.5 Hz), 4.47 (m, 1H,
exo (A)-endo (B) isomer ratio 28/72 is calculated from the
integration curve of protons H9cisA/H9cisB, H9transA/H9transB, and
H1A/H1B; 13C NMR (C5D5N, 22.5 MHz) δ 14.10 (CH3), 22.71
(CH2 alkyl), 27.37 (CH2 alkyl), 29.40 (CH2 alkyl), 29.75 (CH2
alkyl), 31.92 (CH2 alkyl), 42.65 (C10), 62.29 (C6), 70.95 (C4),
71.49 (C2), 78.86 (C5), 80.16 (C3), 88.02 (C1B), 126.55 (C9),
130.20 (C8), 168.22 (C7). Anal. Calcd for C23H43NO6‚0.8H2O:
C, 64.88; H, 10.53; N, 2.80; O, 21.79. Found: C, 64.81; H,
10.87; N, 2.97; O, 21.36.
N -(â-D -G l u c o p y r a n o s y l )-N -(4 -b u t y l -4 -p h e n y l )-
a cr yla m id e (1f) was prepared using the procedure described
above for 1a : quantitative yield of crude 1f, viscous oil;
purification by chromatography (elution: ethyl acetate fol-
lowed by ethyl acetate/ethanol (95:5), two successive columns);
OH6), 4.76 (d, 1HB, H1B, 3J H
) 7.2 Hz), 4.94 (d, 1HA,
-H
OH2A, 3J ) 5 Hz), 4.99 (d, 1H, OH24, 3J ) 5 Hz), 5.07 (db, 1HA,
1
3
3
OH3A, J ) 5 Hz), 5.07 (db, 1HB, OH3B, J ) 5 Hz), 5.16 (d,
1HB, OH2B, 3J ) 5 Hz), 5.38 (d, 1HA, H1A, 3J H 2 ) 8.5 Hz),
-H
1
5.65 (dd, 1HB, H9cisB, 3J ) 11 Hz, 2J ) 2.2 Hz), 5.75 (dd, 1HA,
3
2
3
H
9cisA, J ) 10 Hz, J ) 2 Hz), 6.08 (dd, 1HB, H9transB, J )
2 3 2
16.9 Hz, J ) 2.2 Hz), 6.20 (dd, 1HA, H9transA, J ) 16 Hz, J
) 2 Hz), 6.69 (dd, 1H, H8, 3J ) 17, 10.5 Hz); the exo (A)-endo
(B) isomer ratio 30/70 is calculated from the integration curve
of protons H9cisA/H9cisB, H9transA/H9transB, and H1A/H1B; 13C
NMR (DMSO-d6) δ 13.90 (CH3), 22.04 (CH2 alkyl), 26.41 (CH2
alkylA), 26.73 (CH2 alkylB), 28.42 (CH2 alkyl), 28.66 (CH2
alkyl), 28.77 (CH2 alkyl), 28.99 (CH2 alkyl), 30.72 (CH2 alkylA),

New Reactive Sugar Surfactants
J . Org. Chem., Vol. 63, No. 3, 1998 617
yield 40% (amorphous paste); TLC Rf ) 0.5 (CH2Cl2/MeOH,
over magnesium sulfate. After removal of the solvent under
vacuum, crude 4a (viscous oil) was chromatographed on silica
gel (eluent: CH2Cl2/EtOAc 7/3): yield of pure 4a 77%; TLC Rf
) 0.74 (CH2Cl2/MeOH, 7/3); MS (electrospray) m/z 514.5 (100,
MH+); IR (film, ν cm-1) 3025 (Csp2H), 1751 (CO, ester), 1659
4/1); [R]25 ) +11.00 (c ) 1.5, CH2Cl2), the solution becomes
D
turbid during the measurements; MS (electrospray) m/z 366
(100, M + H+), 388 (20, M + Na+); IR (KBr, ν cm-1) 3377 (OH),
1
3026, 2939, 2870, 2832, 1645 (CO, amide I), 1606 (CdC); H
1
NMR (CD3OD) δ 1.64 (m, 4H, H11, H12), 2.63 (m, 2H, H13),
3.23-3.58 (m, 6H, H2, H3, H4, H5, H10), 3.63 (dd, 1H, H6a, 3J )
5.5 Hz, 2J ) 12 Hz), 3.85 (d, 1H, H6b, 2J ) 12 Hz), 4.87 (d, 1H,
H1B, 3J ) 8.5 Hz), 5.49 (d, 1H, H1A, 3J ) 6.9 Hz), 5.70 (d, 1H,
(CO, amide I), 1620 (CdC); H NMR (CD3OD) δ 0.91 (t, 3H,
3
CH3, J ) 7 Hz), 1.31 (m, 10H, H12-16), 1.93 (s, 3H, COCH3),
1.98 (s, 3H, COCH3), 2.02 (s, 3H, COCH3), 2.04 (s, 3H, COCH3),
3
3.25 (mb, 2H, H10), 4.02 (mb, 1H, H5), 4.18 (dd, 1H, H6a, J )
3
3
2
3
2
H
9cisB, J ) 11.2 Hz), 5.74 (d, 1H, H9cisA, J ) 13.1 Hz), 6.15
3 3
2 Hz, J ) 12 Hz), 4.26 (dd, 1H, H6b, J ) 7 Hz, J ) 12 Hz),
3
3
(d, 1H, H9transB, J ) 17.0 Hz), 6.28 (d, 1H, H9transA, J ) 16.1
Hz), 6.64 (dd, H8A, 3J ) 15.7, 11.1 Hz), 6.73 (dd, H8B, 3J )
17.0, 10.8 Hz), 7.13-7.24 (m, 5H, H14); the exo (A)-endo (B)
isomer ratio equals 27/75 and is calculated from the integration
curve of protons H9transA/H9transB; 13C NMR (CD3OD) δ 29.50,
30.15 and 31.39 (C11, C12), 36.09 and 36.42 (C13A and C13B),
42.97 (C10A), 44.32 (C10B), 62.69 (C6), 71.11, 71.44, 74.81 (C2,
C4), 78.89 (C3 or C5), 80.05 (C3 or C5), 84.36 (C1A), 88.27 (C1B),
126.57, 126.72, 128.07, 129.17, 129.28, 129.45, 129.63, 129.80
and 130.36 (Co, Cp, and Cm), 143.17 (CipsoA), 143.55 (CipsoB),
169.73 (C7A), 170.38 (C7B).
5.10 (t, 1H, H4, J ) 9 Hz), 5.19 (t, 1H, H2, J ) 9 Hz), 5.43 (t,
3
3
1H, H3, J ) 9 Hz), 5.52 (db, 1HB, H1B, J H
) 9 Hz), 5.81
-H
1
2
3
3
(m, 1H, H9cisA + B, J A ) J B ) 11 Hz), 5.94 (db, 1HA, H1A,
3
3J H
) 9 Hz), 6.24 (d, 1HB, H9transB, J ) 17 Hz), 6.31 (d,
3 3
-H
1
2
1HA, H9transA, J ) 16 Hz), 6.65 (dd, 1HA, H8A, J ) 16, 11
Hz), 6.81 (dd, 1HB, H8B, 3J ) 17, 11 Hz); the exo (A)-endo
(B) isomer ratio 50/50 is calculated from the integration curve
of protons H8A/H8B, H9transA/H9transB, and H1A/H1B; 13C NMR
(CD3OD) δ 14.45 (CH3 chain), 20.39 (CH3CO), 20.45 (CH3CO),
20.57 (CH3CO), 20.68 (CH3CO), 23.70 (CH2 alkyl), 27.93 (CH2
alkyl), 28.14 (CH2 alkyl), 29.86 (C12B), 30.32 (CH2 alkyl), 32.49
(CH2 alkyl), 32.95 (CH2 alkyl), 43.6 (C10B or A), 44.7 (C10A or
B), 62.79 (C6B or A), 63.08 (C6 A or B), 69.46 (C4), 70.32 (C2),
74.52 (C5), 74.9 (C3B or A), 75.3 (C3A or B), 82.3 (C1A), 85.55
(C1B), 129.05 (C8B or A), 129.17 (C9B or A), 129.54 (C8A or
B), 130.04 (C9A or B), 169.05 (C7), 170.4 (CO), 171.2 (CO),
171.5 (CO), 172.0 (CO). Anal. Calcd for C25H39NO10: C, 58.48;
H, 7.60; N, 2.73; O, 31.19. Found: C, 58.22; H, 7.90; N, 2.66;
O, 31.28.
N-(â-D-Glu cop yr a n osyl)-N-octylm eth a cr yla m id e (2a )
was prepared using the procedure described above for 1a using
methacryloyl chloride instead of acryloyl chloride; yield of
crude 2a 93%; viscous oil; yield of purification (elution gradient
CH2Cl2/MeOH) 55% (amorphous paste); TLC Rf ) 0.26 (CH2Cl2/
MeOH, 9/1); [R]20 ) +15.33 (c ) 1.5, AcOEt); MS (CI, NH3)
D
m/z 360 (100, MH+); IR (Nujol, ν cm-1) 3500-3200 (OH), 1645
(CO, amide I), 1610 (CdC); 1H NMR (DMSO-d6) δ 0.87 (t, 3H,
CH3 chain, 3J ) 7 Hz), 1.25 (m, 10H, H12-H16), 1.52 (b, 2H,
N-(â-D-(2,3,4,6-Tetr a -O-a cetylglu cop yr a n osyl)-N-(4-bu -
tyl-4-p h en yl)a cr yla m id e (4f) was prepared from 1f (2.6 g)
using the procedure described above for 4a and chromato-
graphed eluting with hexane/EtOAc 2/1. Yield of pure 4f
69.6% (2.64 g), white powder. An analytically pure sample
(2.44 g, 64.3%) was obtained by diffusion of hexane in a CH2Cl2
H
11), 1.86 (s, 3H, CH3 metha), 3.01 (m, 1H, H4), 3.15 (m, 1H,
H3), 3.2-3.5 (mb, 2H, H2, H6b, H10), 3.66 (db, 1H, H6b,
2J )
11.5 Hz), 4.50 (b, 1H, OH6), 4.68 (d, 1H, H1, 3J H 2 ) 8.5 Hz),
-H
1
5.00-5.30 (b, 3H, OH2OH4), 5.11 (s, 1H, H9cis), 5.14 (s, 1H,
H
9trans); 13C NMR (DMSO-d6) δ 13.90 (CH3 alkyl), 20.48 (CH3
metha), 22.04 (CH2 alkyl), 26.68 (CH2 alkyl), 28.24 (CH2 alkyl),
28.62 (CH2 alkyl), 31.21 (CH2 alkyl), 40.47 (C10), 61.09 (C6),
69.88 (C4 and C2), 77.80 (C5), 79.19 (C3), 87.53 (C1), 114.82 (C9),
140.44 (C8), 172.69 (C7).
solution of the product: TLC Rf ) 0.57 (EtOAc); [R]25
)
D
+12.55 (c ) 1.5, EtOAc); MS (electrospray) m/z 534 (100, M +
H+), 551 (40), 556 (20, M + Na+); IR (KBr, ν cm-1) 1754 (CO
1
ester), 1651 (CO, amide I), 1620 (CdC); H NMR (CD3OD) δ
N -(â-D -G lu c o p y r a n o s y l)-N -t e t r a d e c y lm e t h a c r y l-
a m id e (2d ) was prepared using the procedure described above
for 1a using methacryloyl chloride instead of acryloyl chloride;
yield of crude 2d 95%; viscous oil; yield of purification (elution
gradient CH2Cl2/MeOH) 61% (amorphous paste); TLC Rf )
1.61 (m, 4H, H11, H12), 1.91 (s, 3H, CH3), 1.98 (s, 3H, CH3),
2.01 (s, 3H, CH3), 2.03 (s, 3H, CH3), 2.62 (m, 2H, H13), 3.15-
3
3.52 (mb, 2H, H10), 3.99 (mb, 1H, H5), 4.13 (dd, 1H, H6a, J )
1.8 Hz, 2J ) 12.3 Hz), 4.21 (dd, 1H, H6b, 3J ) 4.5 Hz, 2J ) 12.5
Hz), 5.09 (t, 1H, H4, J ) 9.7 Hz), 5.18 (mb, 1H, H2), 5.40 (mb,
0.27 (CH2Cl2/MeOH, 9/1); [R]20 ) +8.6 (c ) 1.5, CH2Cl2); MS
D
1H, H3), 5.51 (mb, 1H, H1B), 5.77 (dd, 2H, H9cisA and B, 3J A
)
(CI, NH3) m/z 360 (100, MH+); IR (Nujol, ν cm-1) 3500-3200
(OH), 1645 (CO, amide I), 1610 (CdC); 1H NMR (DMSO-d6) δ
0.85 (t, 3H, CH3 chain, 3J ) 7 Hz), 1.24 (m, 22H, H12-H22),
1.52 (b, 2H, H11), 1.86 (s, 3H, CH3 metha), 3.09 (m, 1H, H4),
3.14 (m, 1H, H3), 3.2-3.4 (mb, 2H, H2, H6b, H10), 3.66 (d, 1H,
3J B ) 10.3 Hz, 2J A ) 2J B ) 2 Hz), 5.92 (d, 1H, H1A, 3J ) 7 Hz),
3
3
6.24 (d, 1H, H9transB, J ) 16.9 Hz), 6.30 (d, 1H, H9transA, J )
3
18 Hz), 6.57 (dd, 1H, H8A, J ) 10.6, 15.4 Hz), 6.79 (dd, 1H,
H8B, 3J ) 10.6, 16.9 Hz), 7.12-7.28 (m, 5H, HAr); the exo (A)-
endo (B) isomer ratio 50/50 is calculated from the integration
2
3
H
6b, J ) 11.5 Hz)], 4.50 (b, 1H, OH6), 4.68 (d, 1H, H1, J H
-H
1
2
curve of protons H8A/H8B, H9transA/H9transB, and H1A/H1B; 13
C
) 9 Hz), 5.00-5.20 (b, 3H, OH2-OH4), 5.11 (s, 1H, H9cis), 5.14
(s, 1H, H9trans); 13C NMR (DMSO-d6) δ 13.87 (CH3 alkyl), 20.46
(CH3 metha), 22.03 (CH2 alkyl), 26.69 (CH2 alkyl), 28.27 (CH2
alkyl), 28.65 (CH2 alkyl), 28.75 (CH2 alkyl), 29.01 (CH2 alkyl),
31.24 (CH2 alkyl), 40.47 (C10), 61.12 (C6), 69.86 (C4), 69.91 (C2),
77.81 (C5), 79.18 (C3), 87.54 (C1), 114.81 (C9), 140.44 (C8),
172.68 (C7).
NMR (CD3OD) δ 20.40, 20.59 and 20.72 (CH3), 29.51 (C11 or
C12), 30.01 (C11 or C12), 31.89 (C11 or C12), 36.28 (C13A or B),
36.49 (C13A or B), 43.23 and 44.43 (C10A and B), 63.09 (C6),
69.43 (C4), 70.27 (C2), 74.45 (C3), 74.92 (C5A or B), 75.19 (C5A
or B), 82.19 (C1A), 85.50 (C1B), 126.80 (C14), 128.98 (C8A),
129.36 (C9A or B), 129.44 (C14 and C8B), 130.42 (C9A or B),
143.29 (CipsoA or B), 143.61 (CipsoA or B), 168.97 (CO), 170.66
(CO), 171.17 (CO), 171.46 (CO), 172.06 (CO). Anal. Calcd for
N-(â-D-(2,3,4,6-Tetr a -O-a cetylglu cop yr a n osyl)-N-octyl-
a cr yla m id e (4a ). Acetyl chloride (5.6 mL, 78 mmol) was
added dropwise via a dropping funnel to a solution of 1a (2 g,
5.8 mmol) in 50 mL of pyridine cooled at 0 °C with an ice bath
during the addition (addition time: 0.5 h). The reaction
mixture was then stirred for 1 h at room temperature. After
addition of 100 mL of ethyl acetate, the organic phase was
washed with aqueous HCl (1 N, 5 × 50 mL) and a saturated
solution of sodium bicarbonate (3 × 50 mL) and then dried
C
27H35NO10: C, 60.78; H, 6.61; N, 2.62; O, 29.98. Found: C,
60.88; H, 6.67; N, 2.65; O, 29.86.
Ack n ow led gm en t. Solabia and ANRT are grate-
fully acknowledged for a grant to L.R. (Bourse CIFRE).
J O971486D