Sucrose esterification under Mitsunobu conditions: Evidence for the formation of 6-O-acyl-3′,6′-anhydrosucrose besides mono and diesters of fatty acids

Article abstract of DOI:10.1016/j.tetasy.2004.04.021

A series of sucrose monoesters and homogeneous or mixed diesters, which have various chain lengths and saturation levels, were prepared under Mitsunobu conditions with good regioselectivity. Among the anhydro derivatives arising from competitive intramolecular etherification, 3′,6′-anhydrosucrose 6-O-monoesters, which have never been reported, were identified.

Full text of DOI:10.1016/j.tetasy.2004.04.021

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 15 (2004) 1753–1762
Sucrose esterification under Mitsunobu conditions: evidence for the
formation of 6-O-acyl-30,60-anhydrosucrose besides mono and
diesters of fatty acids
ꢀ
ꢁ
*
ꢀ
Valerie Molinier, Juliette Fitremann, Alain Bouchu and Yves Queneau
Laboratoire de Chimie Organique, CNRS UMR 5181, INSA, B^at. J. Verne, 20 avenue A. Einstein, 69621 Villeurbanne Cedex, France
Received 24 March 2004; accepted 16 April 2004
Abstract—A series of sucrose monoesters and homogeneous or mixed diesters, which have various chain lengths and saturation
levels, were prepared under Mitsunobu conditions with good regioselectivity. Among the anhydro derivatives arising from com-
petitive intramolecular etherification, 30,60-anhydrosucrose 6-O-monoesters, which have never been reported, were identified.
ꢀ 2004 Elsevier Ltd. All rights reserved.
1. Introduction
crystalline phases.15 Such studies require materials of
high purity and stability. However, unlike ethers,
sucrose esters can undergo acyl group migrations and in
this respect, esters at primary positions are much more
stable.16;17 We therefore focussed on selective pre-
parative accesses towards sucrose esters at primary
positions.
Sucrose esters are a good example of amphiphilic
derivatives in which both the hydrophilic and the
hydrophobic moieties come from vegetal resources, and
have been acknowledged for their innocuousness. Due
to their physicochemical properties, they are interesting
derivatives, most notably as emulsifiers used in foods
and cosmetics.1–10 They have also recently been shown
to inhibit some transferases.11 We are currently involved
in programs aimed at studying the selectivity of sucrose
chemical transformations12–14 and in this context, we
herein report our new results on the preparation of
esters of defined structure in terms of the degree of
substitution (mono and diesters), regioselectivity and
nature of the hydrophobic part. These compounds have
been committed to further physicochemical studies in
connection with our earlier observations on thermo-
tropic liquid crystal behaviour of amphiphilic sucrose
mono-O-hydroxyalkyl ethers, in which we have shown
how much the position of the chain on the carbohydrate
backbone could determine the geometry of the liquid
Various methods can be used for making esters of
sucrose, with different stereochemical outcomes. Direct
base catalysed transesterification by methyl esters pro-
vides mixtures of isomers essentially composed of esters
at primary positions OH-6, 10 or 60; however they are
often difficult to purify. Furthermore, complex mixtures
of more substituted esters can also form. Methods for
the selective synthesis of primary esters of sucrose in-
clude protease catalysed esterification, which produces
monoesters at the primary OH-10,18–22 esterification at
OH-2 by activated esters followed by migration towards
OH-6,17;23 and Mitsunobu-type esterifications.24–27 We
herein report our own observations on this latter
method, which we have used for preparing a series of
new monoesters at OH-6 and OH-60, homogeneous 6,60-
diesters and mixed 6,60-diesters from monoacylated
substrates, all of which have different chain lengths and
saturation levels. We principally discuss the competition
between dehydration and esterification and the identifi-
cation of new 6-O-acyl-30,60-anhydrosucrose derivatives,
which, because of chromatographic behaviour similar to
that of diesters, imply careful purification when deriva-
tives of physical chemistry grade are needed.
* Corresponding author. Tel.: +33-472-43-61-69; fax: +33-472-43-88-
96; e-mail: yves.queneau@insa-lyon.fr
ꢀ
Present address: Laboratoire des IMRCP, CNRS UMR 5623,
ꢀ
Universite Paul Sabatier, Bat. 2R1, 118 Route de Narbonne, 31062
Toulouse Cedex 4, France.
^
ꢁ
Present address: Tereos S.A., Service Innovation, 12 rue Joseph
ꢀ
Beghin, B.P. 16, 59239 Thumeries, France.
0957-4166/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2004.04.021

1754
V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
2. Results and discussion
chromatography. NMR spectroscopic analysis of the
faster moving chromatography fraction, which contains
the diesters, revealed that another by-product was
present in a significant proportion. Preparative HPLC
allowed full purification of the diester and of the other
product for which mass spectroscopy was consistent
2.1. Reaction of unprotected sucrose
The reaction was first applied to unprotected sucrose 1
using fatty acids 2 of various chain lengths (C8–C22) as
well as unsaturated acids (C12:1, C16:1, C18:1). Using
moderate excesses of reagents (DIAD: 2.7 equiv, PPh3:
2.7 equiv, RCO2H: 2.5 equiv), 6,60-diesters 5 were
formed with good selectivity; the third primary hydroxyl
group (OH-10), close to a quaternary carbon, was
unreactive in this reaction (Scheme 1, Table 1). The
reaction also provided monosubstituted esters at OH-6 3
and OH-60 4 in a 85:15 ratio, constant for all cases. This
is the result of the known faster reaction of unprotected
sucrose at OH-6 and of a faster second esterification of
the 60-O-acyl sucrose derivatives, which still have its
more reactive OH-6 available. Regioisomerically pure
monoesters at OH-6 or OH-60 obtained by this method
are easier to purify (preparative HPLC) than mixtures
obtained by other routes in which esters at other posi-
tions are present, and notably at OH-10, which interfere
in the chromatographic behaviour.
with
a
monoacylated anhydrosucrose derivative
((MþNa) ¼ 529 (2MþNa) ¼ 1035 for a lauric chain).
For this latter product, correlation in the HMBC NMR
spectrum between the carbonyl group and protons H-
6a,b as well as the deshielding of protons H-6a and H-6b
and of carbon C-6, ascertained the acylation position at
O-6. The other patterns of the glucosyl moiety remained
unaffected when compared to a 6-O-acyl sucrose. Con-
versely, noticeable modifications of other patterns were
observed showing that dehydration occurred on the
fructosyl moiety. A characteristic feature was the very
small coupling constants of H-50 with all of its three
neighbours. Also, a widening of the AB systems for
protons H-10a,b and H-60a,b was observed, revealing a
more restricted conformation. However, among these
two CH2 systems, only C-60 exhibited a strongly in-
creased 13C chemical shift as well as a long-range cou-
pling with H-30 (HMBC). The symmetrical effect was
seen between C-30 and H-60b, whereas no long-range
coupling was observed between C-10 and H-40, or be-
tween C-40 and H-10a,b. These couplings, which can only
exist through a newly formed ring, together with the
other data, are consistent with structure 7 in which the
anhydro bridge takes place between the 30- and 60-
positions. The dioxanorbonane representation shown in
Scheme 2 matches with the small coupling constants of
H-50. The 30,40-anhydro exhibits distinctive 13C NMR
chemical shifts for the C-30 and C-40 epoxide ring. Both
anhydro derivatives arose from an attack of OH-3 on
either one or the other oxyphosphonium salts A or B,
both in equilibrium with a pentavalent phosphorane
intermediate,32;33 leading, respectively, to the 30,40 or to
the 30,60 (Scheme 2). The yields of monosubstituted,
The competition between intermolecular esterifications
and intramolecular etherifications results in the side
formation of anhydro derivatives. Until now, only the 6-
O-acyl-30-40 anhydrofructose 6 has been reported in the
presence of a perfluoroalkyl carboxylic acid,26 consistent
with the results described by Guthrie et al. on the for-
mation of a-
D
-glucopyranosyl-3,4-b-D-tagatofuranoside
in the absence of any other nucleophile.28 Although
some 30,60-anhydrosucrose structures have already been
observed,29–31 they have never been mentioned in the
case of esterifications.
Having an intermediate retention factor between
monoesters and diesters, the 6-O-acyl-30,40-anhydro
derivatives 6 can be at least partly purified by silica gel
R
O
OH
OH
O
O
O
HO
HO
OH
O
DIAD, PPh3
HO
HO
HO
OH
O
O
OH
OH
O
OH
R
OH
HO
O
OH
O
OH
+
+
OH
O
OH
DMF, rt., 20 h
OH
O
O
O
OH
R
OH
OH
OH
2a-i
3a-j
1
4a-j
R
O
( )
m
n
O
CH2
n = 6, 8, 10, 14, 16, 18, 20
(m,n) = (3,5), (7,5), (7,7)
a - g: R =
CH3
O
HO
HO
+
OH
OH
O
OH
O
h-j: R = CH
2 ( )
( ) CH3
n
OH
O
O
5a-j
R
O
O
( )
n
( )
n
O
O
O
O
+
+
HO
HO
HO
HO
OH
O
OH
O
OH
OH
OH
O
O
OH
O
O
6a-j
7a-j
Scheme 1.

V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
1755
Table 1. Yields of sucrose and anhydrosucrose esters obtained from unprotected sucrosea
Acid
Monoesters (%)b
Diester (%)c
30,40-Anhydro (%)d
30,60-Anhydro (%)c
Octanoic 2a
Decanoic 2b
3a, 4a (16)
3b, 4b (33)
3c, 4c (35)
3d, 4d (22)
3e, 4e (26)
3f, 4f (27)
3g, 4g (27)
3h, 4h (39)
3i, 4i (34)
3j, 4j (26)
5a (20)
5b (26)
5c (15)
5d (39)
5e (31)
5f (e)
6a (11)
ND
7a (4)
7b (8)
7c (4)
7d (5)
7e (8)
(e)
Lauric 2c
Palmitic 2d
Stearic 2e
6c (11)
6d (9)
6e (6)
(e)
Eicosanoic 2f
Docosanoic 2g
Dodec-5c-enoic 2h
Hexadec-5c-enoic 2i
Octadec-5c-enoic 2j
5f(e)
(e)
(e)
5h (15)
5i (9)
5j (7)
6h (7)
6i (6)
6j (14)
7h (4)
7i (4)
7j (2)
a Conditions: DIAD: 2.7 equiv, PPh3: 2.7 equiv, RCO2H: 2.5 equiv, DMF, rt, 30 h.
b Isolated yields.
c Isolated yields confirmed by HPLC.
d Estimation from intermediate chromatographic fractions masses and NMR analysis.
e Not determined because of multiple purifications due to the low solubility of these derivatives.
O
O
O
( )
( )
( )
n
n
n
O
O
O
O
O
O
HO
HO
HO
HO
HO
HO
OH
O
OH
O
OH
O
O
O
PPh3
O
PPh3
OH
OH
OH
OH
O
O
O
OH
O
OH
HO
A
6a-j
O
O
( )
( )
OH
H4'
n
n
O
O
OH
OGlu
O
O
O
HO
HO
HO
HO
OH
OH
O
OH
H6'b
OH
O
OH
OH
O
O
O
H5'
H6'a
O
OPPh3
OH
B
7a-j
J4',5', J5',6'a, J5',6'b < O.5 Hz
Scheme 2.
disubstituted and anhydro derivatives are given in Table
1 for aliphatic carboxylic acids (octanoic to stearic), as
well as unsaturated ones. Longer acids were also used,
producing slightly more 30,60-anhydro monoesters than
the shorter chains. However, the low solubility of the
starting materials and products in these cases did not
allow accurate control of the actual stoichiometry of the
reaction.
venting us from proving that no transesterifications
occurred. If 10-O-lauroyl sucrose was present in the
starting
mixture,
10-O-lauroyl-6-O-dodec-5c-enoyl
sucrose 9 (7%) also formed. In all cases, the remaining
unreacted monolaurate fraction was simplified, mainly
being composed of the 6-O-isomer. This explains the
higher reactivity of the hydroxyl group OH-6 position in
this type of reaction, as confirmed by kinetic measure-
ments for reactions conducted in parallel starting from
samples containing increasing proportions of the 6-O-
ester, exhibiting a consistent decrease in the rate of
product formation.
2.2. Reaction of sucrose monolaurate
In order to synthesise mixed diesters, with one chain
saturated and the other containing one double bond, the
reaction was applied to sucrose monolaurate samples in
the presence of dodec-5c-enoic acid 2h (Scheme 3, Table
2). From mixtures of sucrose monolaurates, diesters 8a
and 8b were formed together with the 6-O-lauroyl-30,60-
anhydrosucrose 7c derivative. Pure 6-O-lauroylsucrose
led to 6-O-lauroyl-60-O-dodec-5c-enoyl sucrose 8a and
6-O-lauroyl-30,60-anhydrosucrose 7c whereas 60-O-lauro-
ylsucrose only led to the corresponding diester 8b
without formation of any other anhydrofructose deriv-
atives. However, diesters 8a and 8b have identical
chromatographic and spectroscopic properties, pre-
Lauroyl–palmitoyl diesters were also prepared, but the
relative position of the lauric and palmitic chains could
not be ascertained when mixtures of regioisomers of
sucrose laurates were used. Proof that no transesteri-
fication of the starting sucrose ester occurred in the
process was provided by the example of 2-[2-(2-meth-
oxyethoxy)ethoxy]acetic acid 2k, for which 6-O-lauroyl-
60-O-2-[2-(2-methoxyethoxy)ethoxy]acetoxysucrose 10a
and 6-O-2-[2-(2-methoxyethoxy)ethoxy]-acetoxy-60-O-
lauroylsucrose 10b could be separated by semi-
preparative HPLC and identified by 2D NMR using
multiple bond correlation (HMBC). The carbonyl

1756
V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
10a:10b was 27/73 (HPLC) when starting from a sucrose
O
n =14
2d
monolaurate sample containing 6-O-, 10-O- and 60-O-
lauroyl sucrose in the ratio 40/10/33. The higher reac-
tivity of the OH-6 position is highlighted here again.
n
OH
O
( )
OH
3
2h
( )
5
O
OH
2k
O
O
3. Conclusion
O
sucrose monolaurate
R1
The competition between intramolecular esterification
and intramolecular etherification can proceed via two
different reaction pathways in the Mitsunobu esterifi-
DIAD, PPh3,
DMF, rt., 20 h
O
O
cation of sucrose. One forms the already observed a-
glucopyranosyl-3,4-b- -tagatofuranoside, whereas the
D-
O
D
HO
HO
OH
second yields 6-O-acyl-30,60-anhydrosucroses, which
have so far never been described. Being close to the di-
esters in terms of polarity, their isolation requires careful
HPLC purification. Based on these observations,
monoesters and diesters, which have identical or differ-
ent fatty chains with variable lengths and level of satu-
rations, and the new monoacyl-30,60-anhydrosucroses
can be prepared in high purity, a requirement for
structural property relationship studies on sucrose
esters. This has already allowed the observation of a new
transition phase within the smectic A* phase in the case
of 6,60-sucrose distearate.34 Detailed exploration of the
physicochemical properties of these compounds, as pure
materials or in solution, will be reported in due course.
O
C
11H23
OH
O
OH
O
O
O
R2
O
OH
HO
HO
OH
OH
O
OH
O
O
8a R1 = C11, R2 = C11:1
8b R1 = C11:1, R2 = C11
7c
O
8c
R1 = C11, R2 = C15
8d R1 = C15, R2 = C11
( )
5
( )
3
O
( )
10
O
O
O
O
HO
HO
OH
O
OH
O
OH
( )
OH
9
10
10
O
O
4. Experimental
O
HO
HO
OH
4.1. General methods
OH
O
OH
O
O
OH
ꢀ
O
Sucrose was obtained from Beghin-Say. Chromatogra-
O
O
10a
phy solvents were purchased from SDS and Carlo Erba.
HPLC solvents were purchased from SDS. Reactions
were monitored by TLC using glass silica gel plates
(Merck 60 F254). The plates were developed using UV
light and vaporisation with a solution of 10% H2SO4 in
EtOH (v/v). Flash chromatography separations were
performed using Merck Gerudan silica gel Si 60 (40–
63 lm). NMR spectra were recorded on Bruker AC
spectrometers at 75.47 MHz (or 125.77 MHz) for 13C
O
O
O
O
O
10
O
O
HO
HO
OH
OH
O
OH
O
O
( )
OH
10b
10
O
1
NMR and 300.13 MHz (or 500.13 MHz) for H NMR.
LSI-mass spectra were recorded by the Centre de
Scheme 3.
ꢀ
ꢀ
Spectrometrie de Masse of the Universite Claude Ber-
nard (Villeurbanne). Microanalyses were performed by
the Service Central d’Analyse of the CNRS (Vernaison).
Optical rotations were measured with a Perkin Elmer
241 polarimeter. Analytical HPLC analyses were per-
formed at 30 ꢁC using a NH2 spherisorb column
groups could be identified by their long-range coupling
with protons H-6ab or H-60ab and the position of the
oxyethylenic chain, determined by the long-range cou-
pling of the C@O with the CH2 protons at the a-position
of the oxyethylenic chain. The relative proportion of
Table 2. Yields of sucrose and anhydrosucrose esters obtained from sucrose lauratea
Substrate
Acid
Diester (%)b
30,60-Anhydro (%)b
3c
4c
Dodec-5c-enoic 2h
Dodec-5c-enoic 2h
Dodec-5c-enoic 2h
Dodec-5c-enoic 2h
Palmitic 2d
8a (14)
8b (30)
7c (3)
Not formed
7c (5)
7c (3)
3cþ4c (1:1)
8aþ8b (37)
8aþ8b (31)þ9 (7)
8cþ8d (21)
10aþ10b (32)
Mixed monolaurates
Id
Id
7c (3)
ND
2k
a Conditions: DIAD: 2.5 equiv, PPh3: 2.5 equiv, RCO2H: 2 equiv, DMF, rt, 17 h.
b Calculated based on the mass of the chromatographic fraction of the mixture and the measurement of the molar proportions by 1H NMR
spectroscopy analysis. Further semi-preparative HPLC led to pure derivatives.

V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
1757
4.6 · 250 mm (Touzart&Matignon) with a refractometric
detection. The eluting system was a CH3CN/H2O mix-
ture 90/10 to 86/14 v/v (0.8 mL/min) for monoesters and
95/5 v/v for short chain diesters. For long chain diesters
(for solubility reasons) the eluting system was a CH3CN/
THF/H2O mixture 64/30/6 to 40/54/6 v/v. For analytical
HPLC, the injected samples had a concentration of 1–
5 mg/mL. Semi-preparative HPLC separations were
performed on an NH2 spherisorb column 20 · 250 mm
with a refractometric detection. The system was equip-
ped with a 2 mL-injection loop (maximum concentration
of the injected sample: 100 mg/mL). The eluting system
was identical to the one used for analytical HPLC (flow:
20 mL/min).
(C5), 73.4 (C2), 74.7 (C3), 76.2 (C40), 79.5 (C30), 84.1 (C50),
93.7 (C1), 105.5 (C20), 175.8 (1C@O on 6); m=z (LSIMS):
519.2416 (m=zþNa C22H40O12Na requires 519.2417).
4.4. 6-O-Eicosanoylsucrose 3f
25
½aꢁ ¼ þ33 (c 0.5, THF).1H NMR (300 MHz, CDCl3/
D
MeOD): d 0.80–0.96 (3H, m, CH3), 1.15–1.43 (32H, m
(CH2)16),1.52–1.71 (2H, m, CH2b), 2.36 (2H, t,
JCH2–CH2 ¼ 7:5 Hz, CH2a), 3.32 (1H, tþMeOD, J4–3
¼
J4–5 ¼ 9:3 Hz, H4), 3.46 (1H, dd, J2–3 ¼ 9:7 Hz, J2–1
¼
0
0
3:5 Hz, H2), 3.58 (1H, d, J1 b–1 a ¼ 12:5 Hz, H1), 3.66
0
0
(1H, d, J1 a–1 b ¼ 12:5 Hz, H1), 3.69–3.85 (4H, m, H50,
H6=b, H3), 3.94–4.05 (2H, m, H40, H5), 4.08 (1H, d,
0
0
J3 –4 ¼ 8:1 Hz, H30), 4.23 (1H, dd, J6b–6a ¼ 12:2 Hz,
J6b–5 ¼ 4:6 Hz, H6b), 4.38 (1H, dd, J6a–6b ¼ 12:2 Hz,
J6a–5 ¼ 1:7 Hz, H6a), 5.39 (1H, d, J1–2 ¼ 3:5 Hz, H1). 13C
NMR (75 MHz, MeOD): d 14.7 (1CH3), 25.9 (1CH2b),
23.6–30.2–30.4–30.5–30.7–32.9 (16CH2), 35.0 (1CH2a),
C10 and C60 not visible, 64.4 (C6), 71.2 (C4), 71.9 (C5),
72.9 (C2), 74.3 (C3), 75.5 (C40), 79.7 (C30), 83.6 (C50), 93.3
(C1), 105.0 (C20), 175.6 (1C@O on 6). HRMS m=z calcd
for C32H60O12Na (m=zþNa): 659.3982; Found:
659.3985. Anal. Calcd for C32H60O12Æ0.8H2O: C, 59.02;
H, 9.53; O, 31.45; Found: C, 58.93; H, 9.48; O, 31.24.
4.2. Acylation of unprotected sucrose
Sucrose (3.42 g, 9.98 mmol) was dissolved in anhydrous
DMF (80 mL) by stirring under N2 at 70 ꢁC. The mix-
ture was cooled to room temperature before addition of
triphenylphosphine (7.06 g, 2.7 equiv), carboxylic acid
(e.g., lauric acid, 5.00 g, 2.5 equiv) and DMF (20 mL).
After complete dissolution, the medium was cooled to
0 ꢁC and DIAD (5.3 mL, 2.7 equiv) introduced. TLC
showed near total consumption of sucrose after 30 h at
room temperature. After removal of DMF under re-
duced pressure at T ¼ 36–38 ꢁC, the crude residue was
purified by silica gel chromatography [elution gradient:
dichloromethane/acetone/methanol/water 78/10/10/1.5
(A) to 67/15/15/3 v/v (B)]. Successively were collected a
fraction containing the diester and the 30,60-anhydro
derivative (Rf ¼ 0:63 in mixture B), 1.30 g, then the
4.5. 6-O-Docosanoylsucrose 3g
25
D
½aꢁ ¼ þ31 (c 1, THF). HRMS m=z calcd for
C34H64O12Na (m=zþNa): 687.4295; Found: 687.4292.
Anal. Calcd for C34H64O12Æ0.9H2O: C, 59.96; H, 9.74; O,
30.30; Found: C, 60.00; H, 9.87; O, 30.54.
6-O-monoacylated
30,40-anhydrosucrose
derivative
(Rf ꢀ 0:46 in mixture B), and then the monoester frac-
tion (Rf ¼ 0:35 in mixture B, 1.86 g). The monoester
fraction was further subjected to semi-preparative
HPLC to isolate the 6-O-acylsucrose and the 60-O-ac-
ylsucrose. The diester fraction was also repurified by
semi-preparative HPLC to isolate 6-O-acyl-30,60-anhyd-
rosucrose derivative and 6,60-di-O-acylsucrose in pure
forms. Compounds 3a, 3c, 3d, 3e, 4a, 5c and 5d exhib-
ited spectroscopic data identical to those already re-
ported.16;22;24;27;35–37
4.6. 60-O-Palmitoylsucrose 4d
25
½aꢁ ¼ þ42 (c 1, MeOH); dH (300 MHz, MeOD): 0.91
D
(3H, t, JCH3–CH2 ꢀ 7 Hz, CH3), 1.19–1.44 (24H, m
(CH2)12), 1.53–1.71 (2H, m, CH2b), 2.36 (2H, t,
JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.35 (1H, tþMeOD, J4–5
ꢀ
J4–3 ¼ 9:2 Hz, H4), 3.43 (1H, dd, J2–3 ¼ 9:8 Hz, J2–1
¼
0
0
3:8 Hz, H2), 3.60 (1H, d, J1 b–1 a ¼ 12:4 Hz, H1), 3.67
0
0
(1H, d, J1 a–1 b ¼ 12:4 Hz, H1), 3.69–3.79 (2H, m, H6b,
0
0
0
H3), 3.79–3.89 (2H, m, H6a, H5), 3.93 (1H, td, J5 –4
¼
¼
0
0
0
0
0
4.3. 6-O-Decanoylsucrose 3b
J5 –6 a ¼ 7:7 Hz, J5 –6 b ¼ 3:4 Hz, H50), 4.03 (1H, t, J4 –5
0
0
0
0
J4 –3 ¼ 8:0 Hz, H40), 4.11 (1H, d, J3 –4 ¼ 8:0 Hz, H30),
25
D
0
0
0
0
½aꢁ ¼ þ44 (c 1, MeOH); Found: C, 50.65; H, 8.1.
4.32 (1H, dd, J6 b–6 a ¼ 11:7 Hz, J6 b–5 ¼ 3:4 Hz, H6), 4.41
0
0
0
0
C22H40O12Æ1.4H2O requires C, 50.6; H, 8.3%; dH
(300 MHz, MeOD): 0.82–1.03 (3H, m, CH3), 1.18–1.48
(12H, m (CH2)6), 1.51–1.75 (2H, m, CH2b), 2.38 (2H, t,
(1H, dd, J6 a–6 b ¼ 11:7 Hz, J6 a–5 ¼ 7:7 Hz, H6), 5.36
(1H, d, J1–2 ¼ 3:8 Hz, H1); dC (75 MHz, MeOD): 14.8
(1CH3), 26.2 (1CH2b), 24.0–30.5–30.8–30.9–31.1–33.4
(12CH2), 35.2 (1CH2a), 62.8 (C6), 64.1 (C10), 67.2 (C60),
71.8 (C4), 73.5 (C2), 74.5 (C5), 75.0 (C3), 77.2 (C40), 79.3
(C30), 80.9 (C50), 93.7 (C1), 105.8 (C20), 175.7 (1C@O on
60); m=z (LSIMS): 603.3361 (m=zþNa C28H52O12Na
requires 603.3356).
JCH2–CH2 ¼ 7:5 Hz, CH2a), 3.31 (1H, t, J4–3 ¼ J4–5
¼
9:4 Hz, H4), 3.44 (1H, dd, J2–3 ¼ 9:4 Hz, J2–1 ¼ 3:8 Hz,
0
0
H2), 3.60 (1H, d, J1 b–1 a ¼ 12:2 Hz, H1), 3.65 (1H, d,
0
0
J1 a–1 b ¼ 12:2 Hz, H1), 3.74 (1H, t, J4–3 ¼ J3–2 ¼ 9:4 Hz,
H3), 3.77–3.91 (3H, m, H50, H6=b), 3.92–4.08 (2H, m, H40,
0
0
H5), 4.11 (1H, d, J3 –4 ¼ 8:3 Hz, H30), 4.18 (1H, dd,
J6b–6a ¼ 11:9 Hz, J6b–5 ¼ 5:2 Hz, H6b), 4.42 (1H, dd,
J6a–6b ¼ 11:9 Hz, J6a–5 ꢀ 0, H6a), 5.39 (1H, d, J1–2
¼
4.7. 60-O-Stearoylsucrose 4e
3:8 Hz, H1); dC (75 MHz, MeOD): 14.7 (1CH3), 26.3
(1CH2b), 24.0–30.5–30.7–30.9–33.3 (6CH2), 35.2
(1CH2a), 64.2 (C60), 64.4 (C10), 65.0 (C6), 71.9 (C4), 72.2
25
½aꢁ ¼ þ42 (c 0.3, MeOH). 1H NMR (300 MHz,
D
MeOD): dH 0.85–0.99 (3H, m, CH3), 1.20–1.43 (28H, m,

1758
V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
(CH2)14), 1.55–1.70 (2H, m, CH2b), 2.36 (2H, t,
JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.35 (1H, tþMeOD,
J4–3 ¼ J4–5 ¼ 9:4 Hz, H4), 3.42 (1H, dd, J2–3 ¼ 9:8 Hz,
(1C@O on 6). HRMS: m=z calcd for C28H50O12Na
(m=zþNa): 601.3200; Found: 601.3195.
0
0
J2–1 ¼ 3:8 Hz, H2), 3.60 (1H, d, J1 b–1 a ¼ 12:4 Hz, H1),
0
0
3.65 (1H, d, J1 a–1 b ¼ 12:4 Hz, H1), 3.68–3.77 (2H, m,
4.10. 6-O-Octadec-9c-enoylsucrose 3j
H6b, H3), 3.79–3.88 (2H, m, H6a, H5), 3.93 (1H, td,
0
25
D
J5 –4 ¼ J5 –6 a ¼ 7:7 Hz, J5 –6 b ¼ 3:4 Hz, H50), 4.02 (1H, t,
½aꢁ ¼ þ39 (c 0.8, MeOH).1H NMR (300 MHz,
0
0
0
0
0
0
0
0
0
0
0
J4 –5 ¼ J4 –3 ¼ 8:0 Hz, H40), 4.11 (1H, d, J3 –4 ¼ 8:0 Hz,
MeOD): d 0.84–0.99 (3H, m, CH3), 1.17–1.50 (20H, m,
(CH2)10), 1.53–1.73 (2H, m, CH2b), 1.95–2.13 (4H, m,
CH2CH@CHCH2), 2.39 (2H, t, JCH2–CH2 ¼ 7:4 Hz,
0
0
0
0
H30), 4.32 (1H, dd, J6 b–6 a ¼ 11:7 Hz, J6 b–5 ¼ 3:4 Hz,
0
0
0
0
H6), 4.41 (1H, dd, J6 a–6 b ¼ 11:7 Hz, J6 a–5 ¼ 7:5 Hz, H6),
5.36 (1H, d, J1–2 ¼ 3:8 Hz, H1). 13C NMR (75 MHz,
MeOD): dC 14.7 (1CH3), 26.3 (1CH2b), 24.0–30.5–30.8–
30.9–31.1–33.4 (14CH2), 35.2 (1CH2a), 62.8 (C6), 64.1
(C10), 67.2 (C60), 71.8 (C4), 73.6 (C2), 74.5 (C5), 75.0 (C3),
77.2 (C40), 79.3 (C30), 81.0 (C50), 93.8 (C1), 105.8 (C20),
175.8 (1C@O on 60). m=z (LSIMS) (m=zþNa): 631.3672
(C30H56O12Na requires 631.3669).
CH2a),3.31 (1H, ddþMeOD, J4–3 ¼ 9:2 Hz, J4–5
¼
10:0 Hz, H4), 3.43 (1H, dd, J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz,
0
0
H2), 3.58 (1H, d, J1 b–1 a ¼ 12:3 Hz, H1), 3.64 (1H, d,
0
0
J1 a–1 b ¼ 12:3 Hz, H1), 3.68–3.87 (4H, m, H50, H6=b, H3),
0
0
4.07–3.94 (2H, m, H40, H5), 4.10 (1H, d, J3 –4 ¼ 8:3 Hz,
H30), 4.18 (1H, dd, J6a–6b ¼ 11:9 Hz, J6b–5 ¼ 5:4 Hz, H6b),
4.41 (1H, dd, J6a–6b ¼ 11:9 Hz, J6a–5 ¼ 1:9 Hz, H6a), 5.28–
5.44 (3H, m, H1, CH@CH). 13C NMR (75 MHz,
MeOD):
d
14.8 (1CH3), 26.3 (1CH2b), 28.4
4.8. 6-O-Dodec-5c-enoylsucrose 3h
(2CH2aCH@CH), 24.0–30.5–30.6–30.8–30.9–31.1–33.4
(10CH2), 35.2 (1CH2a), 64.2 (C60), 64.3 (C10), 64.9 (C6),
71.8 (C4), 72.2 (C5), 73.3 (C2), 74.7 (C3), 76.1 (C40), 79.4
(C30), 84.1 (C50), 93.6 (C1), 93.6 (C1), 105.4 (C20), 131.1–
131.1 (CH@CH), 175.7 (1C@O on 6). HRMS: m=z calcd
for C30H54O12Na (m=zþNa): 629.3513; Found:
629.3516. Anal. Calcd for C30H54O12Æ1.2H2O: C, 57.34;
H, 9.05; Found: C, 57.27; H, 8.62.
25
D
½aꢁ ¼ þ43 (c 2, MeOH). 1H NMR (300 MHz, MeOD):
d 0.85–0.99 (3H, m, CH3), 1.18–1.45 (8H, m, (CH2)4),
1.68 (2H, q, JCH2–CH2 ¼ 7:3 Hz, CH2b), 1.95–2.19 (4H, m,
CH2CH@CHCH2), 2.40 (2H, t, JCH2–CH2 ¼ 7:3 Hz,
CH2a), 3.31 (1H, tþMeOD, J4–3 ¼ 9:2 Hz, J4–5 ¼ 9:8 Hz,
H4), 3.44 (1H, dd, J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz, H2), 3.59
0
0
0
0
(1H, d, J1 a–1 b ¼ 12:4 Hz, H1), 3.65 (1H, d, J1 a–1 b
¼
12:4 Hz, H1), 3.69–3.89 (4H, m, H3, H50, H6=b), 3.94–4.08
(2H, m, H40, H5), 4.11 (1H, d, J3 –4 ¼ 8:3 Hz, H30), 4.19
(1H, dd, J6b–6a ¼ 11:9 Hz, J6b–5 ¼ 5:3 Hz, H6b), 4.42 (1H,
dd, J6a–6b ¼ 11:9 Hz, J6a–5 ¼ 1:9 Hz, H6a), 5.29–5.49 (3H,
m, H1, CH@CH). 13C NMR (75 MHz, MeOD): d 14.7
(1CH3), 26.3 (1CH2b), 27.8-28.4 (2CH2aCH@CH), 24.0–
30.3–31.0–33.2 (4CH2), 34.6 (1CH2a), 64.2 (C60), 64.3
(C10), 65.0 (C6), 71.9 (C4), 72.2 (C5), 73.4 (C2), 74.7 (C3),
76.1 (C40), 79.5 (C30), 84.1 (C50), 93.6 (C1), 105.5 (C20),
132.2–129.9 (CH@CH), 175.6 (1C@O on 6). HRMS:
m=z calcd for C24H42O12Na (m=zþNa): 523.2754;
Found: 523.2749. Anal. Calcd for C24H42O12Æ1.1H2O: C,
53.15; H, 8.21; O, 38.64; Found: C, 53.07; H, 8.21; O,
38.10.
4.11. 6,60-Di-O-octanoylsucrose 5a
0
0
25
D
1
½aꢁ ¼ þ52 (c 1, THF). H NMR (300 MHz, MeOD): d
0.83–1.00 (2CH3),1.15–1.45 (16H, m, 2(CH2)4), 1.50–1.73
(4H, m, 2CH2b), 2.25–2.50 (4H, m, 2CH2a), 3.25 (1H, t,
J4–3 ¼ 9:0 Hz, J4–5 ¼ 9:6 Hz, H4), 3.43 (1H, dd,
0
0
J2–3 ¼ 9:7 Hz, J2–1 ¼ 3:8 Hz, H2), 3.60 (1H, d, J1 a–1 b
¼
0
0
12:3 Hz, H1), 3.65 (1H, d, J1 a–1 b ¼ 12:3 Hz, H1), 3.72
(1H, t, J3–4 ¼ 9:0 Hz, J3–2 ¼ 9:7 Hz, H3), 3.88–3.98 (1H,
0
0
0
0
m, H50), 4.02 (1H, t, J4 –3 ¼ J4 –5 ¼ 8:0 Hz, H40), 4.03–4.18
(2H, m, H6b, H30, H5), 4.31–4.41 (2H, m, H6=b), 4.45 (1H,
dd, J6a–6b ¼ 11:3 Hz, J6a–5 ¼ 1:3 Hz, H6a), 5.35 (1H, d,
J1–2 ¼ 3:8 Hz, H1).13C NMR (75 MHz, MeOD): d 14.7
(2CH3), 26.3 (2CH2b), 24.0–30.4–33.2 (8CH2), 35.2
(2CH2a), 64.2 (C10), 65.5 (C6), 67.2 (C60), 72.2 (C5, C4),
73.5 (C2), 74.9 (C3), 77.1 (C40), 79.2 (C30), 81.0 (C50), 93.5
(C1), 105.6 (C20), 175.5 (1C@O on 60), 175.8 (1C@O on 6).
HRMS: m=z calcd for C28H50O13Na (m=zþNa): 617.3148;
Found: 617.3148. Anal. Calcd for C28H50O13Æ0.8H2O: C,
55.21; H, 8.54; Found: C, 55.28; H, 8.71.
4.9. 6-O-Hexadec-9c-enoylsucrose 3i
25
D
½aꢁ ¼ þ32 (c 0.2, MeOH). 1H NMR (300 MHz,
MeOD): d 0.80–1.00 (3H, m, CH3), 1.17–1.50 (16H, m,
(CH2)8), 1.53–1.73 (2H, m, CH2b), 1.90–2.15 (4H, m,
CH2CH@CHCH2), 2.39 (2H, t, JCH2–CH2 ¼ 7:4 Hz,
CH2a), 3.31 (1H, ddþMeOD, J4–3 ¼ 9:0 Hz, J4–5
¼
10:0 Hz, H4), 3.43 (1H, dd, J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz,
4.12. 6,60-Di-O-decanoylsucrose 5b
0
0
H2), 3.59 (1H, d, J1 b–1 a ¼ 12:4 Hz, H1), 3.64 (1H, d,
25
D
0
0
0
J1 a–1 b ¼ 12:4 Hz, H1), 3.68–3.87 (4H, m, H3, H5 , H6=b),
½aꢁ ¼ þ49 (c 1, THF). HRMS: m=z calcd for
0
0
3.94–4.07 (2H, m, H40, H5), 4.10 (1H, d, J3 –4 ¼ 8:5 Hz,
H30), 4.18 (1H, dd, J6b–6a ¼ 11:9 Hz, J6b–5 ¼ 5:4 Hz, H6b),
4.41 (1H, dd, J6a–6b ¼ 11:9 Hz, J6a–5 ¼ 2:0 Hz, H6a), 5.26–
5.45 (3H, m, H1, CH@CH).). 13C NMR (75 MHz,
MeOD): d 14.7 (1CH3), 26.3 (1CH2b), 28.4 (2CH2a
CH@CH), 24.0–30.3–30.5–30.6–31.1–33.2 (8CH2), 35.2
(1CH2a), 64.2 (C60), 64.4 (C10), 65.0 (C6), 71.9 (C4), 72.3
(C5), 73.5 (C2), 74.8 (C3), 76.2 (C40), 79.5 (C30), 84.2 (C50),
93.7 (C1), 105.5 (C20), 131.1-131.2 (CH@CH), 175.8
C32H58O13Na (m=zþNa): 673.3775; Found: 673.3779.
Anal. Calcd for C32H58O13Æ0.5H2O: C, 58.25; H, 9.01;
Found: C, 58.26; H, 8.89.
4.13. 6,60-Di-O-stearoylsucrose 5e
25
½aꢁ ¼ þ39 (c 0.4, THF). H NMR (300 MHz, CDCl3/
1
D
MeOD 2/1): d 0.89 (6H, m, 2CH3), 1.28 (56H, m,

V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
1759
2(CH2)14), 1.62 (4H, m, 2CH2b), 2.35 (4H, m, 2CH2a),
3.27 (1H, tþMeOD, J4–3 ¼ J4–5 ¼ 9:4 Hz, H4), 3.46 (1H,
dd, J2–1 ¼ 3:7 Hz, J2–3 ¼ 10:0 Hz, H2), 3.59 (1H, d,
1.50–1.73 (4H, m, 2CH2b), 1.90–2.15 (8H, m,
2CH2CH@CHCH2), 2.27–2.47 (4H, m, 2CH2a), 3.26
(1H, t, J4–3 ¼ 9:0 Hz, J4–5 ¼ 9:6 Hz, H4), 3.43 (1H, dd,
0
0
0
0
0
0
J1 b–1 a ¼ 12:2 Hz, H1), 3.66 (1H, d, J1 a–1 b ¼ 12:6 Hz,
J2–3 ¼9:7 Hz, J2–1 ¼ 3:8 Hz, H2), 3.59 (1H, d, J1 b–1 a
¼
0
H1), 3.72 (1H, t, J3–4 ¼ J3–2 ¼ 9:3 Hz, H3), 3.88–4.10
12:5 Hz, H1), 3.64 (1H, d, J10a–1j ¼ 12:5 Hz, H1), 3.73
b
0
0
0
0
(4H, m, H50, t, J4 –3 ¼ J4 –5 ¼ 7:6 Hz, H40, H5, H30), 4.15
(1H, dd, J6b–6a ¼ 11:8 Hz, J6b–5 ¼ 6:1 Hz, H6b), 4.36 (2H,
m, H6=b), 4.44 (1H, dd, J6a–6b ¼ 11:3 Hz, J6a–5 low, H6a),
5.36 (1H, d, J1–2 ¼ 3:8 Hz, H1). 13C NMR (75 MHz,
MeOD/CDCl3 (4/1 v/v) at 50 ꢁC): d 14.4 (2CH3), 25.4
(2CH2b), 23.2–29.7–29.8–30.0–30.2–32.4 (28CH2), 34.6–
34.7 (2CH2a), 64.4 (C10), 64.5 (C6), 66.2 (C60), 71.1 (C4),
71.4 (C5), 72.4 (C2), 74.2 (C3), 76.8 (C40), 80.1 (C30), 80.3
(C50), 92.5 (C1), 104.7 (C20), 174.7 (1C@O on 60), 175.1
(1C@O on 6). HRMS: m=z calcd for C48H90O13Na
(m=zþNa): 897.6279; Found: 897.6271. Anal. Calcd for
C48H90O13: C, 65.87; H, 10.36; O, 23.76; Found: C,
65.51; H, 10.51; O, 23.26.
(1H, t, J3–4 ¼ 9:0 Hz, J3–2 ¼ 9:7 Hz, H3), 4.05–4.17 (5H,
m, H6b, H30, H5, H40, H50), 4.32–4.41 (2H, m, H6=b), 4.46
(1H, dd, J6a–6b ¼ 11:1 Hz, J6a–5 small, H6a), 5.25–5.47
(5H, m, H1, 2CH@CH). 13C NMR (75 MHz, MeOD): d
14.8 (2CH3), 26.3 (2CH2b), 28.5 (4CH2aCH@CH), 24.0–
30.4–30.5–30.7–31.2–33.3 (16CH2), 35.2 (2CH2a), 64.3
(C10), 65.5 (C6), 67.2 (C60), 72.2 (C5, C4), 73.5 (C2), 74.9
(C3), 77.1 (C40), 79.2 (C30), 81.0 (C50), 93.4 (C1), 105.6
(C20), 131.1–131.2 (4CH, 2CH@CH), 175.4 (1C@O on
60), 175.8 (1C@O on 6). HRMS: m=z calcd for
C44H78O13Na (m=zþNa): 837.5340; Found: 837.5338.
Anal. Calcd for C44H78O13Æ1.2H2O: C, 63.16; H, 9.68;
Found: C, 63.12; H, 9.54.
4.14. 6,60-Di-O-eicosanoylsucrose 5f
4.17. 6,60-Di-O-octadec-9c-enoylsucrose 5j
25
D
25
D
1
½aꢁ ¼ þ37 (c 0.2, THF). 13C NMR (75 MHz, MeOD/
½aꢁ ¼ þ35 (c 2, THF). H NMR (300 MHz, MeOD): d
CDCl3 (4/1 v/v) at 50 ꢁC): d 14.4 (2CH3), 25.4 (2CH2b),
23.1–29.7–29.8–30.0–30.2–32.4 (32CH2), 34.5–34.6
(2CH2a), 64.4 (C10), 64.5 (C6), 66.2 (C60), 71.0 (C4), 71.3
(C5), 72.4 (C2), 74.1 (C3), 76.8 (C40), 80.1 (C30), 80.3 (C50),
92.5 (C1), 104.6 (C20), 174.6 (1C@O on 60), 175.1 (1C@O
on 6). HRMS: m=z calcd for C52H98O13Na (m=zþNa):
841.5653; Found: 841.5649. Anal. Calcd for C52H98O13:
C, 67.06; H, 10.61; Found: C, 67.26; H, 10.52.
0.83–1.00 (6H, m, 2CH3), 1.17–1.47 (40H, m, 2(CH2)10),
1.53–1.73 (4H, m, 2CH2b), 1.95–2.15 (8H, m,
2CH2CH@CHCH2), 2.37–2.47 (4H, m, 2CH2a), 3.26
(1H, t, J4–3 ¼ 9:0 Hz, J4–5 ¼ 9:6 Hz, H4), 3.44 (1H, dd,
0
0
J2–3 ¼ 9:7 Hz, J2–1 ¼ 3:8 Hz, H2), 3.58 (1H, d, J1 b–1 a
¼
0
0
12:4 Hz, H1), 3.65 (1H, d, J1 a–1 b ¼ 12:4 Hz, H1), 3.73
(1H, t, J3–4 ¼ 9:0 Hz, J3–2 ¼ 9:7 Hz, H3), 3.89–4.17 (5H,
m, H6b, H30, H5, H40, H50), 4.32–4.42 (2H, m, H6=b), 4.46
(1H, dd, J6a–6b ¼ 11:3 Hz, J6a–5 small, H6a), 5.25–5.45
(5H, m, H1, 2CH@CH). 13C NMR (75 MHz, MeOD): d
14.9 (2CH3), 26.3 (2CH2b), 28.5 (4CH2aCH@CH), 24.1–
30.6–30.7–30.8–31.0–31.2–33.4 (20CH2), 35.2 (2CH2a),
64.3 (C10), 65.5 (C6), 67.2 (C60), 72.2 (C5, C4), 73.4 (C2),
74.9 (C3), 77.2 (C40), 79.3 (C30), 81.0 (C50), 93.4 (C1),
105.6 (C20), 131.1–131.2 (4CH, 2CH@CH), 175.3
(1C@O on 60), 175.7 (1C@O on 6). HRMS: m=z calcd
for C48H86O13Na (m=zþNa): 893.5966; Found:
893.5969.
4.15. 6,60-Di-O-dodec-5c-enoylsucrose 5h
25
D
½aꢁ ¼ þ42 (c 2, THF). 1H NMR (300 MHz, MeOD): d
0.92 (6H, t, JCH3–CH2 ꢀ 7 Hz, 2CH3), 1.22–1.45 (16H, m,
2(CH2)4), 1.61–1.76 (4H, m, 2CH2b), 1.98–2.17 (8H, m,
2CH2CH@CHCH2), 2.31–2.49 (4H, m, 2CH2a), 3.26
(1H, t, J4–3 ¼ 9:0 Hz, J4–5 ¼ 9:8 Hz, H4), 3.43 (1H, dd,
J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz, H2), 3.59 (1H, d,
0
0
0
J1 b–1 a ¼ 12:3 Hz, H1), 3.65 (1H, d, J10a–1j ¼ 12:3 Hz,
b
H1), 3.72 (1H, t, J3–4 ¼ 9:0 Hz, J3–2 ¼ 9:8 Hz, H3), 3.89–
0
0
0
0
3.98 (1H, m, H50), 4.02 (1H, t, J4 –3 ¼ J4 –5 ¼ 8:2 Hz,
4.18. 6-O-Octanoyl-a-
D-tagatofuranoside 6a
D
-glucopyranosyl-3,4-anhydro-b-
0
0
H40), 4.10 (1H, d, J3 –4 ¼ 8:2 Hz, H30), 4.06–4.17 (2H, m,
H6b, H5), 4.34–4.43 (2H, m, H6=b), 4.46 (1H, dd,
J6a–6b ¼ 11:3 Hz, J6a–5 ¼ 1:3 Hz, H6a), 5.28–5.50 (5H, m,
H1, 2CH@CH). 13C NMR (75 MHz, MeOD): d 14.8
(2CH3), 26.2–26.3 (2CH2b), 27.8–28.5 (4CH2aCH@CH),
24.0–30.3–31.1–33.2 (8CH2), 34.6 (2CH2a), 64.3 (C10),
65.5 (C6), 67.2 (C60), 72.1 (C5, C4), 73.4 (C2), 74.8 (C3),
77.1 (C40), 79.2 (C30), 80.9 (C50), 93.4 (C1), 105.5 (C20),
132.0–132.0–130.1–130.2 (2CH@CH), 175.2 (1C@O on
60), 175.6 (C@O on 6). HRMS: m=z calcd for
C36H62O13Na (m=zþNa): 725.4088; Found: 725.4091.
Anal. Calcd for C36H62O13. 1.1H2O: C, 59.83; H, 8.95;
Found: C, 59.78; H, 8.84.
(Rf ¼ 0:46 in dichloromethane/acetone/methanol/water
1
67/15/15/3 v/v). H NMR (300 MHz, MeOD): d 0.90–
1.00 (3H, m, CH3), 1.17–1.45 (8H, m (CH2)4), 1.53–1.73
(2H, m, CH2b), 2.34 (2H, t, JCH2–CH2 ¼ 7:4 Hz, CH2a),
3.29 (1H, dd, J4–3 ¼ 10:0 Hz, J4–5 ¼ 8:9 Hz, H4), 3.41
(1H, dd, J2–3 ¼ 9:7 Hz, J2–1 ¼ 3:8 Hz, H2), 3.60–3.77
(5H, m, H6=b, H1, H3, H1), 3.81–3.88 (2H, m, H40, H30),
3.98–4.14 (2H, m, H50, H5), 4.23 (1H, dd,
J6a–6b ¼ 11:7 Hz, J6a–5 ¼ 6:2 Hz, H6b), 4.37 (1H, dd,
J6a–6b ¼ 11:7 Hz, J6a–5 ¼ 2:2 Hz, H6a), 5.40 (1H, d,
J1–2 ¼ 3:8 Hz, H1). 13C NMR (75 MHz, MeOD): d 14.7
(CH3), 26.2 (CH2b), 23.9–30.3–30.4–33.1 (4CH2), 35.2
(CH2a), 56.5 (C30), 58.2 (C40), 62.0 (C60), 65.2 (C6), 65.7
(C10), 71.9 (C5), 72.2 (C4), 73.3 (C2), 75.0 (C3), 78.9 (C50),
94.1 (C1), 105.5 (C20), 175.7 (1C@O on 6). HRMS: m=z
calcd for C20H34O11Na (m=zþNa): 473.1999; Found:
473.1999.
4.16. 6,60-Di-O-hexadec-9c-enoylsucrose 5i
25
½aꢁ ¼ þ38 (c 1, THF).1H NMR (300 MHz, MeOD): d
D
0.80–1.00 (6H, m, 2CH3), 1.15–1.47 (32H, m, 2(CH2)8),

1760
V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
4.19. 6-O-Octanoyl-a-
D
-glucopyranosyl-3,6-anhydro-b-
82.4 (C50), 93.9 (C1), 110.1 (C20), 175.3 (1C@O on 6).
HRMS: m=z calcd for C28H50O11Na (m=zþNa): 585.3251;
Found: 585.3254. Anal. Calcd for C28H50O11Æ0.2H2O: C,
59.39; H, 8.97; Found: C, 59.33; H, 8.91.
D
-fructofuranoside 7a
25
½aꢁ ¼ þ76 (c 1, THF). H NMR (300 MHz, MeOD): d
1
D
0.90–1.00 (3H, m, CH3), 1.23–1.43 (8H, m, (CH2)4),
1.53–1.70 (2H, m, CH2b), 2.34 (2H, t, JCH2–CH2 ¼ 7:4 Hz,
CH2a), 3.29 (1H, ddþMeOD, J4–3 ¼ 9:1 Hz, J4–5
¼
4.22. 6-O-Stearoyl-a-
fructofuranoside 7e
D
-glucopyranosyl-3,6-anhydro-b-D-
9:8 Hz, H4), 3.50 (1H, dd, J2–3 ¼ 9:5 Hz, J2–1 ¼ 3:7 Hz,
0
0
H2), 3.61 (1H, d, J1 b–1 a ¼ 12:8 Hz, H1), 3.72 (1H, t,
25
D
1
0
0
J3–4 ¼ 9:1 Hz, J3–2 ¼ 9:5 Hz, H3), 3.93 (1H, dd, J6 b–6 a
¼
¼
½aꢁ ¼ þ62 (c 0.4, THF). H NMR (300 MHz, CDCl3/
0
0
0
0
8:2 Hz, J6 b–5 ¼ 1:4 Hz, H6), 4.00 (1H, d, J1 a–1 b
MeOD 1/1): d 0.92 (3H, t, JCH2–CH3 ꢀ 7 Hz, CH3), 1.20–
1.45 (28H, m (CH2)14), 1.55–1.70 (2H, m, CH2b), 2.34
(2H, t, JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.29 (1H, tþMeOD,
12:8 Hz, H1), 4.08–4.24 (4H, m, H6b, H6, H5, H30), 4.29
(1H, ‘s’, H50), 4.36–4.48 (2H, m, H6a, H40), 5.39 (1H, d,
J1–2 ¼ 3:7 Hz, H1). 13C NMR (75 MHz, MeOD): d 14.7
(CH3), 26.3 (CH2b), 23.9–30.4–30.4–33.1 (4CH2), 35.3
(CH2a), 63.0 (C10), 65.4 (C6), 72.0 (C60), 72.1 (C4), 72.4
(C5), 73.7 (C2), 75.1 (C3), 78.2 (C40), 79.5 (C30), 83.0 (C50),
94.5 (C1), 110.6 (C20), 175.7 (1C@O on 6). HRMS: m=z
calcd for C20H34O11Na (m=zþNa): 473.1999; Found:
473.1998. Anal. Calcd for C20H34O11Æ0.8H2O: C, 51.67;
H, 7.72; Found: C, 51.71; H, 7.53.
J4–3 ¼ 9:2 Hz, J4–5 ¼ 9:6 Hz, H4), 3.50 (1H, dd, J2–3
¼
0
0
9:6 Hz, J2–1 ¼ 3:8 Hz, H2), 3.61 (1H, d, J1 b–1 a ¼ 12:7 Hz,
H1), 3.75 (1H, t, J3–4 ¼ 9:2 Hz, J3–2 ¼ 9:6 Hz, H3), 3.93
0
0
0
0
0
(1H, dd, J6 b–6 a ¼ 8:2 Hz, J6 b–5 ¼ 1:4 Hz, H6 b), 4.00
0
0
0
(1H, d, J1 a–1 b ¼ 12:7 Hz, H1 a), 4.08–4.24 (4H, m, H6b,
H6, H5, H30), 4.29 (1H, ‘s’, H50), 4.35–4.50 (2H, m, H6a,
H40), 5.39 (1H, d, J1–2 ¼ 3:8 Hz, H1). HRMS: m=z calcd
for C30H54O11Na (m=zþNa): 613.3564; Found:
613.3569. Anal. Calcd for C30H54O11Æ1H2O: C, 59.19; H,
9.27; O, 31.54; Found: C, 58.99; H, 9.08;, O, 31.10.
4.20. 6-O-Lauroyl-a-
fructofuranoside 7c
D
-glucopyranosyl-3,6-anhydro-b-D-
4.23. Acylation of sucrose monolaurate
25
½aꢁ ¼ þ68 (c 1, THF). H NMR (300 MHz, MeOD): d
1
D
0.92 (3H, t, JCH2–CH3 ꢀ 7 Hz, CH3), 1.23–1.43 (16H, m
Sucrose monolaurate (mixture of isomers (6/10/6040/10/
33), 1.00 g, 1.9 mmol) was dissolved in anhydrous DMF
(20 mL) under N2 at room temperature. Triphenyl-
phosphine (1.26 g, 2.5 equiv) and the carboxylic acid
(dodec-5c-enoic, 0.84 mL, 2 equiv) were then added.
After complete dissolution, the mixture was cooled to
0 ꢁC and DIAD (0.94 mL, 2.5 equiv) introduced under
N2. After 17 h at room temperature, TLC showed the
formation of less polar products without total con-
sumption of the sucrose monolaurate. DMF was
removed under reduced pressure at T ¼ 36–38 ꢁC and
the crude residue submitted to silica gel chromatography
(elution gradient: dichloromethane/acetone/methanol/
water 78/10/10/1.5 (A) to 67/15/15/3 (B) v/v). A first
fraction was isolated (Rf ¼ 0:60 in solvent B, 10-O-do-
dec-5c-enoyl-6-O-lauroylsucrose, 94 mg, 7%) and the
main products then isolated (Rf ¼ 0:49 in solvent B, 6-
O-dodec-5c-enoyl-60-O-lauroylsucrose and 6-O-lauroyl-
60-O-dodec-5c-enoylsucrose, 453 mg, 34%). The diester
was further purified by semi-preparative HPLC to
remove the anhydro derivative contaminant.
(CH2)8), 1.55–1.70 (2H, m, CH2b), 2.34 (2H, t,
JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.29 (1H, ddþMeOD, J4–3
¼
9:2 Hz, J4–5 ¼ 9:8 Hz, H4), 3.50 (1H, dd, J2–3 ¼ 9:6 Hz,
0
0
J2–1 ¼ 3:8 Hz, H2), 3.61 (1H, d, J1 b–1 a ¼ 12:8 Hz, H1),
3.72 (1H, dd, J3–4 ¼ 9:2 Hz, J3–2 ¼ 9:6 Hz, H3), 3.93 (1H,
0
0
0
0
dd, J6 b–6 a ¼ 8:2 Hz, J6 b–5 ¼ 1:4 Hz, H6), 4.01 (1H, d,
0
0
J1 a–1 b ¼ 12:8 Hz, H1), 4.10–4.23 (4H, m, H6b, H6, H5,
H30), 4.29 (1H, ‘s’, H50), 4.36–4.47 (2H, m, H6a, H40), 5.39
(1H, d, J1–2 ¼ 3:8 Hz, H1). 13C NMR (75 MHz, MeOD): d
14.7 (CH3), 26.3 (CH2b), 33.4–31.0–30.9–30.8–30.7–30.5–
24.0 (8CH2), 35.3 (CH2a), 63.0 (C10), 65.5 (C6), 72.0 (C60),
72.1 (C4), 72.4 (C5), 73.7 (C2), 75.2 (C3), 78.2 (C40), 79.5
(C30), 83.1 (C50), 94.5 (C1), 110.6 (C20), 175.7 (1C@O on 6).
HRMS: m=z calcd for C24H42O11Na (m=zþNa): 529.2625;
Found: 529.2625. Anal. Calcd for C24H42O11Æ0.4H2O: C,
56.10; H, 8.40; Found: C, 56.07; H, 8.34.
4.21. 6-O-Palmitoyl-a-
D
-glucopyranosyl-3,6-anhydro-b-
D
-fructofuranoside 7d
25
D
1
½aꢁ ¼ þ67 (c 1, THF). H NMR (300 MHz, CDCl3/
MeOD 1/1): d 0.87 (3H, t, JCH2–CH3 ꢀ 7 Hz, CH3), 1.15–
1.40 (24H, m (CH2)12), 1.53–1.67 (2H, m, CH2b), 2.32
(2H, t, JCH2–CH2 ¼ 7:5 Hz, CH2a), 3.29 (1H, ddþMeOD,
4.24. 6-O-Palmitoyl-60-O-lauroylsucrose 8c and 6-O-lau-
royl-60-O-palmitoylsucrose 8d
J4–3 ¼ 9:2 Hz, J4–5 ¼ 9:4 Hz, H4), 3.53 (1H, dd, J2–3
¼
1H NMR (300 MHz, MeOD/CDCl3 25/75): d 0.77–0.95
(6H, m, 2CH3), 1.15–1.40 (40H, m (CH2)20), 1.50–1.67
(4H, m, 2CH2b), 2.25–2.43 (4H, m, 2CH2a), 3.26 (1H,
dd, J4–3 ¼ 9:0 Hz, J4–5 ¼ 10:0 Hz, H4), 3.46 (1H, dd,
0
0
9:6 Hz, J2–1 ¼ 3:8 Hz, H2), 3.62 (1H, d, J1 b–1 a ¼ 12:8 Hz,
H1), 3.75 (1H, dd, J3–4 ¼ 9:2 Hz, J3–2 ¼ 9:6 Hz, H3), 3.92
0
0
0
0
(1H, dd, J6 b–6 a ¼ 8:3 Hz, J6 b–5 ¼ 1:3 Hz, H6), 3.99 (1H,
0
0
0
0
d, J1 a–1 b ¼ 12:8 Hz, H1), 4.07–4.25 (4H, m, H6b, H6, H5,
H30), 4.30 (1H, ‘s’, H50), 4.36–4.45 (2H, m, H6a, H40), 5.39
(1H, d, J1–2 ¼ 3:8 Hz, H1). 13C NMR (75 MHz, MeOD): d
14.6 (CH3), 25.7 (CH2b), 23.5–30.0–30.2–30.4–30.5–32.8
(12CH2), 35.0 (CH2a), 62.5 (C10), 65.1 (C6), 71.5 (C60), 71.5
(C4), 71.7 (C5), 72.9 (C2), 74.6 (C3), 77.6 (C40), 78.9 (C30),
J2–3 ¼ 9:6 Hz. J2–1 ¼ 3; 7 Hz, H2), 3.57 (1H, d, J1 b–1 a ¼
0
0
0
12:4 Hz, H1 b), 3.66 (1H, d, J1 a–1 b ¼ 12:4 Hz, H1), 3.76
(1H, dd, J3–4 ¼ 9:0 Hz, J3–2 ¼ 9:6 Hz, H3), 3.88–4.08
(4H, m, H5, H30, H40, H50), 4.17 (1H, dd, J6b–6a ¼ 11:8 Hz,
J6b–5 ¼ 5:9 Hz, H6b), 4.23–4.45 (3H, m, H6a, H6=b), 5.36
(1H, d, J1–2 ¼ 3:7 Hz, H1). 13C NMR (75 MHz, MeOD):

V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
1761
d 14.6 (2CH3), 25.6 (2CH2b), 23.4–29.9–30.1–30.3–30.4–
32.7 (20CH2), 34.7–34.8 (2CH2a), 64.3 (C10), 64.7 (C6),
66.6 (C60), 71.2 (C4), 71.4 (C5), 72.6 (C2), 74.1 (C3), 76.6
(C40), 79.7 (C30), 80.3 (C50), 92.6 (C1), 104.6 (C20), 175.0
(1C@O on 60), 175.4 (1C@O on 6). HRMS: m=z calcd
for C40H74O13Na (m=zþNa): 785.5027; Found:
785.5023. Anal. Calcd for C40H74O13Æ0.7H2O: C, 61.94;
H, 9.80; O, 28.26; Found: C, 61.88; H, 9.79; O, 28.06.
(CH2)8), 1.55–1.70 (2H, m, 2CH2b), 2.36 (2H, t,
JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.24 (1H, dd, J4–3 ¼ 8:9 Hz,
J4–5 ¼ 9:9 Hz, H4), 3.36–3.42 (3H, m, CH3O), 3.43 (1H,
dd, J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz, H2), 3.53–3.78 (8H, m,
4CH2O, H3, H1=b), 3.89–3.98 (1H, m, H50), 4.02 (1H, dd,
0
0
0
0
J4 –3 ¼ 8:2 Hz, J4 –5 ¼ 8:5 Hz, H40), 3.91–3.98 (1H, m,
0
0
H5), 4.10 (1H, d, J3 –4 ¼ 8:1 Hz, H30), 4.18 (1H, dd,
J6a–6b ¼ 11:7 Hz, J6b–5 ¼ 6:6 Hz, H6b), 4.23–4.32 (2H, m,
CH2aO), 4.33–4.41 (2H, m, H6=b), 4.55 (1H, dd,
J6a–6b ¼ 11:7 Hz, J6a–5 ¼ 1:8 Hz, H6a), 5.35 (1H, d,
J1–2 ¼ 3:8 Hz, H1). 13C NMR (125 MHz, MeOD): d 14.5
(CH3), 26.0 (CH2b), 23.8–30.2–30.5–30.7–33.1 (8CH2),
34.9 (CH2a), 59.1 (CH3O), 64.0 (C10), 65.7 (C6), 66.9
(C60), 69.2 (CH2aO), 71.3–71.8 (3CH2O), 71.9 (C5), 71.9
(C4), 72.9 (1CH2O), 73.2 (C2), 74.6 (C3), 76.7 (C40), 78.8
(C30), 80.7 (C50), 93.1 (C1), 105.4 (C20), 172.32 (1C@O
oxyethylenic on 6), 175.3 (1C@O laurate on 60). HRMS:
m=z calcd for C31H56O16Na (m=zþNa): 707.3466;
Found: 707.3464. Anal. Calcd for C31H56O16: C, 52.72;
H, 8.54; O, 38.74; Found: C, 52.67; H, 8.30; O, 38.52.
4.25. 6-O-Dodec-5c-enoyl-60-O-lauroylsucrose 8a and 6-
O-lauroyl-60-O-dodec-5c-enoylsucrose 8b
1H NMR (500 MHz, MeOD): d 0.88–0.97 (6H, m,
2CH3), 1.25–1.42 (24H, m (CH2)12), 1.58–1.75 (4H, m,
2CH2b), 2.01–2.16 (4H, m, CH2CH@CHCH2), 2.32–
2.49 (4H, m, 2CH2a), 3.27 (1H, dd, J4–3 ¼ 9:1 Hz,
J4–5 ¼ 9:8 Hz, H4), 3.45 (1H, dd, J2–3 ¼ 9:5 Hz, J2–1
¼
0
0
3:9 Hz, H2), 3.61 (1H, d, J1 b–1 a ¼ 12:3 Hz, H1), 3.65
0
0
(1H, d, J1 a–1 b ¼ 12:3 Hz, H1), 3.74 (1H, dd, J3–4
¼
9:1 Hz, J3–2 ¼ 9:5 Hz, H3), 3.98–3.92 (1H, m, H50), 4.03
0
0
0
0
(1H, t, J4 –3 ¼ J4 –5 ¼ 8:2 Hz, H40), 4.16–4.05 (3H, m,
H6b, H30, H5), 4.42–4.35 (2H, m, H6=b), 4.47 (1H, dd,
J6a–6b ¼ 11:7 Hz, J6a–5 ¼ 1:6 Hz, H6a), 5.39 (3H, m, H1
and CH@CH). 13C NMR (125 MHz, MeOD): d 14.8
(2CH3), 26.3 (2CH2b), 28.5–27.8 (2CH2aCH@CH), 24.0–
30.4–30.5–30.8–30.9–31.0–31.1–33.2–33.4 (12CH2), 34.6–
35.2 (2CH2a), 64.3 (C10), 65.5 (C6), 67.2 (C60), 72.1 (C5,
C4), 73.4 (C2), 74.8 (C3), 77.1 (C40), 79.2 (C30), 81.0 (C50),
93.4 (C1), 105.6 (C20), 130.0–131.2 (CH@CH), 175.4
(1C@O on 60), 175.6 (1C@O on 6). HRMS: m=z calcd for
C30H54O11Na (m=zþNa): 727.4245; Found: 727.4248.
Anal. Calcd for C36H64O13Æ0.9H2O: C, 59.96, H, 9.20;
Found: C, 59.95, H, 9.13.
4.28. 10-O-Dodec-5c-enoyl-6-O-lauroylsucrose 9
25
D
1
½aꢁ ¼ þ31 (c 0.4, THF). H NMR (500 MHz, MeOD):
d 0.80–1.00 (6H, m, 2CH3), 1.20–1.50 (24H, m, (CH2)12),
1.55–1.75 (4H, m, 2CH2b), 2.00–2.20 (4H, m,
CH2CH@CHCH2), 2.30–2.50 (4H, m, 2CH2a), 3.31 (1H,
ddþMeOD, J4–3 ¼ 9:4 Hz, J4–5 and, H4), 3.42 (1H, dd,
J2–3 ¼ 9:8 Hz, J2–1 ¼ 3:8 Hz, H2), 3.68 (1H, dd,
J3–4 ¼ 9:4 Hz, J3–2 ¼ 9:8 Hz, H3), 3.73–3.85 (3H, m, H6=b
,
H50), 4.00–4.08 (2H, m, H5, H40), 4.09 (1H, d,
0
0
0
0
J3 –4 ¼ 8:5 Hz, H30), 4.14 (1H, d, J1 b–1 a ¼ 12:0 Hz, H1),
4.19 (1H, dd, J6b–6a ¼ 11:8 Hz, J6b–5 ¼ 5:5 Hz, H6b), 4.38
0
(1H, d, J1 a–b ¼ 12:0 Hz, H1), 4.43 (1H, dd,
4.26. 6-O-Lauroyl-60-O-2-[2-(2-methoxyethoxy)ethoxy]-
acetoxysucrose 10a
J6a–6b ¼ 11:8 Hz, J6a–5 ¼ 1:9 Hz, H6a), 5.41 (3H, m, H1,
CH@CH). 13C NMR (125 MHz, MeOD): d 14.7 (2CH3),
26.3 (2CH2b), 27.8–28.5 (2CH2aCH@CH), 24.0–30.4–
30.5–30.7–30.8–30.9–31.0–31.1–33.3–33.4 (12 CH2),
34.6–35.3 (2CH2a), 64.0 (C10, C60), 65.0 (C6), 72.0 (C4),
72.3 (C5), 73.3 (C2), 74.7 (C3), 75.6 (C40), 79.0 (C30), 84.3
(C50), 94.3 (C1), 104.4 (C20), 129.9–132.3 (CH@CH),
175.0 (1C@O on 10), 175.7 (1C@O on 6). HRMS: m=z
calcd for C30H54O11Na (m=zþNa): 727.4245; Found:
727.4245.
25
½aꢁ ¼ þ11 (c 7, THF). 1H NMR (500 MHz, MeOD): d
D
0.92 (3H, t, JCH2–CH3 ꢀ 7 Hz, CH3), 1.25–1.43 (16H, m
(CH2)8), 1.57–1.70 (2H, m, CH2b), 2.41 (2H, t,
JCH2–CH2 ¼ 7:4 Hz, CH2a), 3.27 (1H, t, J4–3 ¼ J4–5
¼
9:3 Hz, H4), 3.35–3.41 (3H, m, CH3O), 3.43 (1H, dd,
J2–3 ¼ 9:7 Hz, J2–1 ¼ 3:8 Hz, H2), 3.52–3.60 (2H, m,
CH2O), 3.60–3.70 (6H, m, H1=b, 2CH2O), 3.70–3.76 (3H,
m, H3, CH2O), 3.92–3.99 (1H, m, H50), 4.00–4.09 (2H,
m, H5, H40), 4.09–4.15 (2H, m, H6b, H30), 4.19–4.26 (2H,
m, CH2aO), 4.40–4.51 (3H, m, H6a, H6=b), 5.34 (1H, d,
J1–2 ¼ 3:8 Hz, H1). 13C NMR (125 MHz, MeOD): d 14.5
(CH3), 26.0 (CH2b), 23.8–25.3–30.5–30.7–30.8–33.1
(8CH2), 34.9 (CH2a), 59.2 (OCH3), 63.9 (C10), 65.2 (C6),
67.0 (C60), 69.2 (1CH2aO),71.3–71.6 (3CH2O), 71.9 (C4),
71.9 (C5), 73.0 (1CH2O), 73.2 (C2), 74.6 (C3), 76.7 (C40),
78.8 (C30), 80.5 (C50), 93.3 (C1), 105.4 (C20), 172.1 (1C@O
oxyethylenic on 60), 175.5 (1C@O laurate on 6). HRMS:
m=z calcd for C31H56O16Na (m=zþNa): 707.3466;
Found: 707.3465.
Acknowledgements
ꢀ
This work was achieved in the former Beghin-Say––
CNRS research facility in Villeurbanne (CNRS UMR
143). Financial support from these institutions as well as
ꢀ
a grant to VM from Beghin-Say and ANRT (contrat
CIFRE) is gratefully acknowledged.
References and notes
4.27. 6-O-2-[2-(2-Methoxyethoxy)ethoxy]acetoxy-60-O-
lauroylsucrose 10b
1. Hill, K.; Rhode, O. Fett/Lipid 1999, 101, 25–33.
2. Baker, I. J. A.; Matthews, B.; Suares, H.; Krodkiewska, I.;
Furlong, D. N.; Grieser, F.; Drummond, C. J. J. Surf.
Deterg. 2000, 3, 1–11.
25
½aꢁ ¼ þ9 (c 9, THF). H NMR (500 MHz, MeOD): d
1
D
0.91 (3H, t, JCH2–CH3 ꢀ 7 Hz, CH3), 1.25–1.40 (16H, m
3. Nakamura, S. Inform. 1997, 8, 866–874.

1762
V. Molinier et al. / Tetrahedron: Asymmetry 15 (2004) 1753–1762
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