Transesterification of Sucrose in Organic Medium: Study of Acyl Group Migrations

Article abstract of DOI:10.1081/CAR-120026466

The tendency of the acyl groups located on the glucose part of sucrose fatty acid esters to undergo intramolecular migrations in organic medium and the regioselectivity of some transesterifications of sucrose were investigated by HPLC, in situ NMR spectroscopy and preparative methods. Extensive acylation on secondary positions of the glucose moiety followed by migrations is general for base catalysed transesterification. The stability of 3- and 6-O-acyl derivatives, two isomers being thermodynamically favored compared to others, was studied in a series of conditions. It is shown that the presence of water catalyzes the migration of the ester at OH-3 towards OH-6 in organic basic medium, whereas the ester at OH-6 appears more stable under either acidic or basic conditions.

Full text of DOI:10.1081/CAR-120026466

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Transesterification of Sucrose in Organic Medium:
Study of Acyl Group Migrations
Valérie Molinier a , Krzysztof Wisniewski a , Alain Bouchu a , Juliette Fitremann a & Dr. Yves
Queneau a b
a Laboratoire de Sucrochimie, CNRS UMR 143, Béghin‐Say, C.E.I., 66 Boulevard Niels Bohr, BP
2132, 69603, Villeurbanne Cedex, France
b Laboratoire de Chimie Organique, INSA de Lyon, Bât. J. Verne, 20 Avenue Albert Einstein,
69621, Villeurbanne Cedex, France
Version of record first published: 23 Feb 2007.
To cite this article: Valérie Molinier , Krzysztof Wisniewski , Alain Bouchu , Juliette Fitremann & Dr. Yves Queneau (2003):
Transesterification of Sucrose in Organic Medium: Study of Acyl Group Migrations , Journal of Carbohydrate Chemistry, 22:7-8,
657-669
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JOURNAL OF CARBOHYDRATE CHEMISTRY
Vol. 22, Nos. 7 & 8, pp. 657–669, 2003
Transesterification of Sucrose in Organic Medium:
Study of Acyl Group Migrationsy
Vale´rie Molinier, Krzysztof Wisniewski, Alain Bouchu,
*
Juliette Fitremann, and Yves Queneau
Laboratoire de Sucrochimie, Villeurbanne Cedex, France
ABSTRACT
The tendency of the acyl groups located on the glucose part of sucrose fatty acid esters
to undergo intramolecular migrations in organic medium and the regioselectivity of
some transesterifications of sucrose were investigated by HPLC, in situ NMR
spectroscopy and preparative methods. Extensive acylation on secondary positions of
the glucose moiety followed by migrations is general for base catalysed trans-
esterification. The stability of 3- and 6-O-acyl derivatives, two isomers being ther-
modynamically favored compared to others, was studied in a series of conditions. It is
shown that the presence of water catalyzes the migration of the ester at OH-3 towards
OH-6 in organic basic medium, whereas the ester at OH-6 appears more stable under
either acidic or basic conditions.
Key Words: Sucrose; Regioselective esterification; Acyl group migration; In situ
NMR.
yThis paper is dedicated to Professor Ge´rard Descotes on the occasion of his 70th birthday, in
acknowledgement of his accomplishments in the field of carbohydrate chemistry, and of his
continuing efforts for developing the use of renewable sugars for chemistry.
*
Correspondence: Dr. Yves Queneau, Laboratoire de Chimie Organique, INSA de Lyon, Baˆt.
J. Verne, 20 Avenue Albert Einstein, 69621 Villeurbanne Cedex, France; E-mail: queneau@
univ-lyon1.fr.
657
DOI: 10.1081/CAR-120026466
0732-8303 (Print); 1532-2327 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

658
Molinier et al.
INTRODUCTION
Finding renewable raw materials for chemistry, alternative to fossil resources, is of
considerable interest. In this context, the use of carbohydrates, and notably of sucrose as
starting material, has been extensively studied.a[5] Among derivatives having industrial
applications, the amphiphilic sucrose fatty acid esters, also known as sucroesters, have
interesting physicochemical properties in particular as emulsifiers, and are used in the
food and cosmetic fields.[6–10] An important issue in their synthesis is the control of the
degree of substitution, which is connected with their emulsifying properties.[11–17] This
search for selective processes has been part of our work in the field of the use of
sucrose as a chemical,[18–21] with emphasis on the search for regioselective reactions,
as the regioselectivity is the source of control of the degree of substitution. Indeed,
when one of the 8 hydroxyl groups exhibits a preeminent reactivity towards an
electrophilic species, the second substitution occurs in a slower manner, thus allowing
trapping of a low substituted derivative. This regioselectivity has, in fact, to be
considered as a chemoselectivity of one alcohol function compared to another.
Even though the kinetic relative reactivity of sucrose hydroxyl groups is now rather
well understood, in the case of esters, the potency of acyl groups to migrate perturbs
the easy correlation between the regiochemical distribution of the substituents and the
relative reactivity of the sucrose 8 hydroxyl groups. Although most base catalyzed
transesterifications lead finally to primary esters, the preeminent reactivity of OH-2 has
been established,[22–26] with examples consistent with spectroscopic and theoretical
studies. Even in aqueous medium, we showed that the perturbation of the hydrogen
bond network by solvation did not prevent secondary OH-groups, and notably OH-2,
from being esterified first, before migrations to OH-3 and OH-6 could occur,[27,28] as in
organic medium.
In a program aimed at the understanding of the influence of the position of the
chain on the physicochemical properties of sucrose amphiphilic derivatives, we showed
recently that the thermotropic behavior of sucrose amphiphilic ethers was very
dependant on the geometry of the connection between the polar and the hydrophobic
parts of the molecule.[29] In order to obtain similar information in the case of sucrose
esters, we needed to ascertain the stability of some isomers, and in particular that of
derivatives esterified at OH-3 and OH-6. We report here our study of the migration
pathways in the case of the preparation of sucrose fatty acid esters in organic medium,
as well as some aspects helping the preparation of 6-O-acyl sucrose derivatives using
the sequential migration method.[30]
RESULTS AND DISCUSSION
To study the stability of the acyl group located on the glucose moiety of sucrose,
we synthesized samples of 2-O, 3-O-, and 6-O-alkanoyl sucroses (Scheme 1), using the
transesterification of N-acylthiazolidinethiones, as described by Plusquellec,[22,30–32]
followed by preparative HPLC for full identification of pure isomers. A catalytic
[1 –4]
aFor reviews in the field of the use of carbohydrates as chemicals, see Refs.
.

Transesterification of Sucrose
659
Scheme 1.
amount of a base such as sodium hydride was reported to provide good yields of
sucrose esters, with a predominance of the isomer at OH-2. To obtain supplementary
information on the regioisomeric distribution evolution, we studied the effect of other
bases, and notably of solid salts such as carbonates and phosphates (Table 1). Starting
from N-decanoylthiazolidinethione, moderate to good yields of monodecanoyl sucrose
were obtained. The best yield was observed for the reaction achieved in the presence of
two equivalents of dipotassium hydrogenophosphate. In this case, the monoesters were
essentially the isomers at position 2 and 3. The structure (in particular the position of
the esterified OH) of these regioisomers was ascertained by 1H and 13C NMR
spectroscopy. It is interesting to note that only moderate amounts (less than 10%) of
esters at position 1’ and 6’ were present in the mixture, indicating again the superior

660
Molinier et al.
Table 1. Transesterification of sucrose (2 equiv) with N-decanoylthiazolidinethione (1.2 equiv)
in DMF.
Regioisomeric distribution %
Monoester
3 yield % 3-O- 3’-O- 4-O- 2-O- 4’-O- 6-O- 1’-O- 6’-O-
Conditions base
(equiv), T, t
K2HPO4 (2), rt, 21 h
K2CO3 (0.5), rt,
40 min
71
47
16
36
15
14
54
27
1
1
4
9
1
10
8
1
K2CO3 (0.5), rt, 6 h
Li2CO3 (0.5), rt, 24 h
Cs2CO3 (1), rt, 20 min
Cs2CO3 (1), ꢀ 10°C,
18 h
65
53
46
54
27
13
34
16
12
20
14
9
12
57
14
5
2
0
2
2
27
3
15
5
3
1
2
4
19
48
15
16
reactivity of the glucosyl moiety. In the presence of lithium carbonate, little amounts of
1’ or 6’ esters were also observed. Potassium and cesium carbonates led to more
complex mixtures, resulting from extensive acyl transfer to OH-3 and OH-6, and a
significantly larger amount of esterification at position 1’ (ca. 15% of the mixture).
These ratios are very similar to those described for the reaction involving catalytic
sodium hydride. The use of catalytic butyllithium gave sucrose laurates in similar
yields and regioselectivity. In this case, the N-acylthiazolidinethione was compared
with cyanoethyl-, methylthioethyl- and methylesters as acyl donnors (Table 2), con-
firming the unique ability of the N-acylthiazolidinethiones to afford 2-O-acylated suc-
rose esters as the major product, in connection with the role of the thiazolidinetione
anion as the active base in the medium.[22] With the other acylating agents, the major
ester is formed at OH-6. This, as well as the small proportion of esters at 1’ and 6’,
indicates that the reaction is again rather selective on the glucose moiety. This can
either be the result of a selective esterification at OH-2 followed by migrations to OH-3
and OH-6, or a direct selective esterification at OH-6, without concomitant esteri-
fication at the other primary positions 6’ and 1’. This latter mechanism is less likely to
Table 2. Transesterification of sucrose with different acyl donors in DMF, in the presence of
catalytic butyl lithium (sucrose/C11H23COX/BuLi = 1/1/0.05, 3 h, rt).
Monoester regioisomeric distribution %
Monoester Diester
X
4 yield % yield % 3-O- 3’-O- 4-O- 2-O- 4’-O- 6-O- 1’-O- 6’-O-
48
11
12
14
66
1
1
6
–
CNCH2O–
MeSCH2-
CH2O–
37
11
14
8
12
16
5
6
6
9
4
4
57
52
10
7
6
6
MeO–
11
–
15
7
6
6
53
6
7

Transesterification of Sucrose
661
Table 3. Lithium carbonate catalyzed transesterification of sucrose with various N-
acylthiazolidinethiones (sucrose/N-acylthiazolidinethione/Li2CO3 = 1/1/0.05, 3 h, rt).
Monoester regioisomeric distribution %
Monoester
R
(yield) %
3-O-
3’-O- 4-O-
2-O-
4’-O-
6-O-
1’-O-
6’-O-
C7H15
C9H19
C11H23
C13H27
C15H31
C17H35
2 (86)
3 (65)
4 (81)
5 (76)
6 (49)
7 (91)
2
10
9
11
17
14
16
15
16
72
59
63
58
61
65
1
1
3
3
3
4
4
3
10
9
1
1
1
8
1
14
11
10
<1
<1
1
7
<1
<1
–
8
5
occur as we observed that in some cases, even though the reaction was less selective at
OH-6, the other isomers present were essentially those at OH-2 and OH-3.
The lithium carbonate catalyzed reaction was used to prepare a series of sucrose
esters (C8, C10, C12, C14, C16, C18) starting from the corresponding N-acylthiazolidi-
nethiones, in moderate to good yields, and with consistently the same distribution of
regioisomers (Table 3).
We then studied in detail the outcome of the reaction of sucrose with N-
lauroylthiazolidine thione using Et3N/DBU, as reported for the final obtention of 6-O-
esters.[30] Our data confirm that indeed migration to OH-6 occurs only when DBU is
added, but also that esters at OH-3 are present in the final mixture, and this in a larger
amount after work-up than expected from HPLC-monitoring during the course of the
reaction (Table 4). The inconsistency between HPLC and NMR data revealed the
important role of the aqueous work-up. This led us to look more closely at the behavior of
esters at OH-3 and OH-6 at the early stage of the reaction under these conditions. The 3-
O-monolaurate was treated under conditions allowing the isomerization to the OH-6
position (Table 5). The samples which were analyzed by HPLC without any work-up
revealed the presence of the 6-O-ester. It was hypothesized that, when base is still
present, water in the HPLC eluent promotes the very fast acyl migration, together with
extensive hydrolysis. On the contrary, after acidification, aqueous work-up and
Table 4. Transesterification of sucrose with N-lauroylthiazolidinethione in DMF, in the presence
of Et3N/DBU. (sucrose/N-lauroylthiazolidinethione/Et3N = 1/0.2/1.5, 30 h then + DBU (1.5 equiv),
15 h, rt). Yield 4: 45%.
Monoester regioisomeric distribution %
Conditions
3-O-
3’-O- 4-O-
2-O-
4’-O-
6-O-
1’-O-
6’-O-
aliquot of the medium at the
end of the reaction
7
5
0
5
64
10
8
after acidification and
extractions
14
13
5
5
6
5
4
4
58
59
8
8
5
5
after column-chromatography
and freeze-drying

662
Molinier et al.
Table 5. Behavior of 3-O-sucrose monolaurate (4a) placed in the reaction isomerization
conditions (0.1 M in DMF, in the presence of DBU).
Monoester regioisomeric distribution % (100 mL of the
medium + 1 mL CH3CN/H2O 90/10)
Conditions
3-O-
3’-O- 4-O-
2-O-
4’-O-
6-O-
1’-O-
6’-O-
Starting sample
+ DBU (1 equiv)
95
13
9
5
5
5
6
3
0
2
0
–
–
–
0
0
73
76
71
11
0
7
0
–
–
1
0
id. after 15 min
id. after 35 min
2
9
9
72
3
13
11
0
after 40 min, + AcOH and
evaporation of DMF
Starting sample
73
11
3
20
5
0
2
2
4
4
3
3
67
38
0
9
0
2
+ DBU (1.3 equiv)
evaporation of DMF
without neutralisation
4
11
39
Table 6. Behavior of 6-O-sucrose monolaurate (trial 1) and 6-O-sucrose monodecanoate (3c)
(trial 2) placed in the same isomerization conditions.
Monoester regioisomeric distribution % (50 mL of the
medium + 0.5 mL (trial 1) and 1 mL (trial 2) CH3CN/H2O 90/10)
Conditions
3-O-
3’-O- 4-O-
2-O-
4’-O-
6-O-
1’-O-
6’-O-
Starting sample
0
0
0
0
1
0
0
1
1
0
0
1
0
0
0
0
84
86
86
85
0
0
0
0
14
14
14
13
+ AcOH (50 mL), t = 0
after 1 h, + AcOH (50 mL)
After 2 h, evaporation
of DMF
Starting sample
0
10
0
0
5
5
0
2
0
0
0
0
100
83
0
0
0
0
0
2
+ DBU (0.8 equiv), t = 0
after 15 min, + AcOH
(60 mL)
93
id. after 5h15
id. after 1 night
0
0
0
0
0
5
0
0
2
0
0
0
100
100
92
0
0
0
0
0
0
after 1 night, + DBU
(1.2 equiv), t’ = 0
after 10 min, + AcOH
(100 mL)
after 2 h30, + AcOH
(50 mL)
0
0
0
4
5
4
0
0
0
0
0
0
96
95
95
0
0
0
0
0
1
after 24 h, evaporation
of DMF

Transesterification of Sucrose
663
Figure 1. 1H NMR monitoring of the migration from the 3 position.

664
Molinier et al.
purification, mostly unchanged 3-O-ester, as indicated by the deshielding of the
characteristic triplet at 5.23 ppm (J3–4 = J3–2 = 9.7 Hz), together with a significant
proportion (13%) of 2-O-ester, were detected in the final mixture. Sucrose ester self
transesterifications to diesters and sucrose, both observed as traces, could not account for
the important changes in the regioisomeric distribution. However, when no acidic
treatment is performed before evaporation of the solvent, extensive late transesterification
is observed, leading to a lower yield of a mixture of esters, essentially at OH-6, 1’ and 6’.
As shown in Table 6, it was ascertained that treatment of the 6-O-ester in all
possible conditions (with or without DBU and with or without reacidification) did not
lead to any reverse migration of the acyl moiety towards the secondary hydroxyl
groups. It can thus be concluded that the rate of the migration from OH-3 to OH-6 is
dramatically accelerated in the presence of water and occurs during the aqueous work-
up. The same process occurred during HPLC samples preparations (MeCN-water as a
solvent). The absolute HPLC integrations confirm that migration and hydrolysis take
place on the HPLC column during analysis, since the total integration of the
monoesters decreased strongly after addition of DBU, before increasing to the starting
value after acidification of the medium.
Those results were confirmed by studying the outcome of the reaction by in situ
NMR in deuterated DMSO, allowing us to follow directly in the medium the presence of
the various isomers. It was possible to observe that indeed no significant acyl migration
from OH-3 to OH-6 or OH-2 occurred in the presence of DBU and absence of water.
When a small amount of water is added to a mixture of 3-O-monolaurate and DBU in
DMSO-d6, the characteristic signals of H2 and H6a become distinctively visible and
increase upon prolongation of the reaction (Figure 1), indicating that the addition of
water triggers off the migration process under these conditions. These observations,
together with those reported until now,[30,32] reflect an easy migration from OH-2 to OH-
3 (reversible but in favor of 3-O-esters), and a slow migration from OH-3 to OH-6. The
6-O-acylated derivative appears nearly as stable as its regioisomers acylated at positions
1’ and 6’, respectively, which were prepared by other methods.[33,34] These observations
could also be the effect of changes in the conformation of sucrose due to the presence of
water[35] which would modify the relative distances between OH-groups and therefore
the rates of migrations in an aqueous medium compared to an organic one.
CONCLUSION
In conclusion, the stability of acyl groups at OH-3 and OH-6 of sucrose has been
studied by in situ NMR spectroscopy in DMSO-d6, together with HPLC analysis and
preparative experiments. Notably, it was shown that, unlike the rapid OH-2 to OH-3
acyl migration, the acyl transfer from OH-3 to OH-6 is less favored. However, the
latter is accelerated by the presence of water. Attention must therefore be paid to
possibly misleading HPLC data, owing to the aqueous conditions in use. In the absence
of any acidic work-up, only the 6-O-ester is obtained. However, depending on the
reaction time, various proportions of the 2-O, 3-O and 6-O esters are obtained after
acidic aqueous work-up. The ester at OH-6 is shown to be much more stable. We have
also described the use of lithium carbonate as the base for the transesterification of the
N-acylthiazolidinethione leading also to esters at OH-2 as the major product. These
results provide useful complement to this method for which we have confirmed the

Transesterification of Sucrose
665
synthetic usefulness for the preparation of defined sucrose derivatives with ester
functions on the glucose moiety.
EXPERIMENTAL
General methods. Sucrose was obtained from Be´ghin-Say. Chromatography and
HPLC solvents were purchased from SDS. Reactions were monitored by TLC using
aluminium or 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 mm). NMR spectra were recorded on Bruker AC spectrometers at 75.47 MHz
1
for 13C NMR and 300.13 MHz for H NMR. Mass spectra were recorded by the Centre
de Spectrome´trie de Masse of the Universite´ Claude Bernard (Villeurbanne). Micro-
analyses were performed by the Service Central d’Analyse of the CNRS (Solaize).
Optical rotations were measured with a Perkin Elmer 241 polarimeter. Analytical HPLC
analyses were performed at 30°C, using an NH2 spherisorb column 4.6 ꢁ 250 mm
(Touzart & Matignon), eluted with a CH3CN/H2O mixture 90/10 to 86/14 v/v (0.8 mL/
min) and with refractometric detection.
Preparation of sucrose decanoates (3) in the presence of solid salts. The
mixture of sucrose (2 equiv), N-decanoylthiazolidinethione (1.2 equiv) and solid base
was stirred in anhyd DMF at rt for 24 h. The mixture was then filtered and analyzed by
HPLC. The monoesters were obtained after evaporation of the solvent and purification
on a silica gel column using a 56/20/20/4 (v/v) mixture of CH2Cl2/Me2CO/MeOH/H2O.
Preparation of sucrose laurates (4) in the presence of catalytic BuLi. Sucrose
(1 equiv) was dissolved in anhyd DMF, before the appropriate acyl donor (1 equiv) and
BuLi (0.05 equiv) were added at rt. The mixture was stirred at the same temperature for
3 h. The base was then neutralised with acetic acid, and the solvent removed under
reduced pressure. The residue was partitioned between a phosphate buffer (pH 7) and a
mixture of ethyl acetate/1-butanol 1/1 (v/v). After evaporation of the solvents, sucrose
esters were purified by silica gel column chromatography using a 56/20/20/4 (v/v)
mixture of CH2Cl2/Me2CO/MeOH/H2O.
Preparation of sucrose esters of fatty acids (2–7). Sucrose (6.4 g, 20 mmol)
was dissolved in anhyd DMF (60 mL). The appropriate N-acylthiazolidinethione (10
mmol) was added, followed by lithium carbonate (740 mg, 10 mmol) at room
temperature. The mixture was stirred for 24 h at rt. The base was then filtered and the
solvent removed under reduced pressure. The residue was chromatographed on a silica
gel column using a 56/20/20/4 (v/v) mixture of CH2Cl2/Me2CO/MeOH/H2O.
Purification of isomers 3a, 3b, 3c and 4a, 4b, 4c. Monoesters 3 and 4 were
further purified by semi-preparative chromatography to obtain pure isomers 3a, 3b, 3c
and 4a, 4b, 4c. Separations were performed on an NH2 spherisorb column 20 ꢁ 250 mm
with refractometric detection. The system was equipped with a 2 mL-injection loop
(concentration of the injected sample: 100 mg/mL). The eluting system was a CH3CN/
H2O mixture 90/10 to 86/14 (v/v) (flow: 20 mL/min).

666
Molinier et al.
Data for the mono-O-decanoylsucroses and mono-O-lauroylsucroses. Anal.
Calcd were performed on the 6-O-isomer. Optical rotations, HRMS (FAB +) and NMR
data are given for each isomer, in order of elution from the semi-preparative HPLC (3-
O-, 2-O-, 6-O-).
3-O-Decanoylsucrose (3a). [a]D + 61 (c 1, MeOH). 1H NMR (300 MHz,
MeOD): d 0.91 (3H, m, CH3), 1.31 (12H, m, (CH2)6), 1.66 (2H, m, CH2b), 2.41 (2H,
m, CH2a), 3.53 (1H, t, J4–3 = J4–5 = 9.6 Hz, H-4), 3.60 (1H, dd, J2–1 = 3.8 Hz,
J2 – 3 = 10.0 Hz, H-2), 3.62 (1H, d, J1’a – 1’b = 12.1 Hz, H-1’b), 3.68 (1H, d,
J1’a–1’b = 12.2 Hz, H-1’a), 3.78–3.93 (6H, m, H-5’, H-6’a, H-6’b, H-5, H-6a, H-6b),
4.05 (1H, t, J4’–3’ = J4’–5’ = 7.9 Hz, H-4’), 4.13 (1H, d, J3’–4’ = 8.3 Hz, H-3’), 5.23 (1H, t,
J3–4 = J3–2 = 9.6 Hz, H-3), 5.45 (1H, d, J1–2 = 3.8 Hz, H-1). 13C NMR (75 MHz,
MeOD): d 14.7 (1CH3), 26.3 (1CH2b), 24.0, 30.4, 30.7, 30.7, 30.8, 33.3 (6CH2), 35.6
(1CH2a), 62.1, 63.7 (C-6, C-6’), 64.3 (C-1’), 69.6 (C-4), 71.7 (C-5), 74.5 (C-2), 76.0
(C-3), 76.9 (C-4’), 79.5 (C-3’), 84.1 (C-5’), 93.8 (C-1), 105.8 (C-2’), 175.9 (1C = O).
HRMS: m/z calcd for C22H40O12Na: 519.2417. Found: 519.2417.
2-O-Decanoylsucrose (3b). (contains 9% of 3a). [a]D + 66 (c 1, MeOH). 1H
NMR (300 MHz, MeOD): d 0.91 (3H, m, CH3), 1.31 (12H, m, (CH2)6), 1.65 (2H, m,
CH2b), 2.41 (2H, m, CH2a), 3.41 (1H, d, H-1’b), 3.45 (1H, t, J4–3 = J4–5 = 9.8 Hz, H-
4), 3.53 (1H, d, J1’a–1’b = 12.1 Hz, H-1’a), 3.65–3.93 (7H, m, H-3, H-5, H-5’, H-6’a, H-
6’b, H-6a, H-6b), 4.03 (1H, t, J4’–3’ = J4’–5’ = 8.1 Hz, H-4’), 4.20 (1H, d, J3’–4’ = 8.7
Hz, H-3’), 4.63 (1H, dd, J2–1 = 3.7 Hz, J2–3 = 10.3 Hz, H-2), 5.55 (1H, d, J1–2 = 3.6
Hz, H-1). 13C NMR (75 MHz, MeOD): d 14.7 (1CH3), 26.0 (1CH2b), 23.9, 30.5, 30.6,
30.7, 30.8, 33.2 (6CH2), 35.3 (1CH2a), 62.3, 63.6 (C-6, C-6’), 63.4 (C-1’), 71.7 (C-4),
72.1 (C-5), 74.3 (C-2), 74.5 (C-3), 75.4 (C-4’), 77.6 (C-3’), 83.8 (C-5’), 91.0 (C-1),
105.5 (C-2’), 175.5 (1C = O). HRMS: m/z calcd for C22H40O12Na: 519.2417. Found:
519.2418.
6-O-Decanoylsucrose (3c). [a]D + 44 (c 1, MeOH). 1H NMR (300 MHz, MeOD):
d 0.91 (3H, m, CH3), 1.32 (12H, m, (CH2)6), 1.63 (2H, m, CH2b), 2.38 (2H, m, CH2a),
3.31 (1H, t, J4–3 = J4–5 = 9.4 Hz, H-4), 3.44 (1H, dd, J2–1 = 3.8 Hz, J2–3 = 9.6 Hz, H-
2), 3.60 (1H, d, J1’a–1’b = 12.2 Hz, H-1’b), 3.65 (1H, d, J1’a–1’b = 12.1 Hz, H-1’a), 3.74
(1H, t, J3–4 = J3–2 = 9.3 Hz, H-3), 3.77–3.91 (3H, m, H-5’, H-6’a, H-6’b), 3.92–4.08
(2H, m, H-4’, H-5), 4.11 (1H, d, J3’–4’ = 8.3 Hz, H-3’), 4.18 (1H, dd, J6a–6b = 12.0 Hz,
J6b–5 = 5.2 Hz, H-6b), 4.42 (1H, dd, J6a–6b = 10.9 Hz, H-6a), 5.39 (1H, d, J1–2 = 3.77
Hz, H-1); 13C NMR (75 MHz, MeOD): d 14.7 (1CH3), 26.3 (1CH2b), 24.0, 30.5, 30.7,
30.9, 33.3 (6CH2), 35.2 (1CH2a), 64.2 (C-6’), 64.4 (C-1’), 65.0 (C-6), 71.9 (C-4), 72.2
(C-5), 73.4 (C-2), 74.7 (C-3), 76.2 (C-4’), 79.5 (C-3’), 84.1 (C-5’), 93.7 (C-1), 105.5 (C-
2’), 175.8 (1C = O). HRMS: m/z calcd for C22H40O12Na: 519.2417. Found: 519.2416.
Anal. Calcd for C22H40O12.1.4H2O: C, 50.64; H, 8.27. Found: C, 50.65; H, 8.08.
3-O-Lauroylsucrose (4a). [a]D + 54 (c 1, MeOH). Lit.[22] 1H NMR (300 MHz,
MeOD): d 0.91 (3H, m, CH3), 1.31 (16H, m, (CH2)8), 1.66 (2H, m, CH2b), 2.41 (2H, m,
CH2a), 3.53 (1H, t, J4–3 = J4–5 = 9.7 Hz, H-4), 3.59 (1H, dd, J2–1 = 3.8 Hz, J2–3 = 10.0
Hz, H-2), 3.62 (1H, d, J1’a–1’b = 12.2 Hz, H-1’b), 3.68 (1H, d, J1’a–1’b = 12.2 Hz, H-1’a),
3.71–3.87, 3.88–3.98 (6H, 2 m, H-6’a, H-6’b, H-5, H-6a, H-6b, H-5’), 3.99–4.09 (1H,

Transesterification of Sucrose
667
m, H-4’), 4.10 (1H, d, J3’–4’ = 8.3 Hz, H-3’), 5.23 (1H, t, J3–4 = J3–2 = 9.7 Hz, H-3),
5.45 (1H, d, J1–2 = 3.8 Hz, H-1). 13C NMR (75 MHz, MeOD): d 14.7 (1CH3), 26.3
(1CH2b), 24.0, 30.5, 30.8, 30.9, 31.0, 33.4 (8CH2), 35.6 (1CH2a), 62.1, 63.7 (C-6, C-6’),
64.3 (C-1’), 69.7 (C-4), 71.7 (C-5), 74.5 (C-2), 76.0 (C-3), 77.0 (C-4’), 79.5 (C-3’), 84.2
(C-5’), 93.9 (C-1), 105.8 (C-2’), 175.9 (1C = O). HRMS: m/z calcd for C24H44O12Na:
547.2730. Found: 547.2731.
2-O-Lauroylsucrose (4b). [a]D + 63 (c 1, MeOH). Lit.[22] 1H NMR (300 MHz,
MeOD): d 0.91 (3H, m, CH3), 1.31 (16H, m, (CH2)8), 1.66 (2H, m, CH2b), 2.43 (2H,
m, CH2a), 3.39 (1H, d, J1’a–1’b = 11.7 Hz, H-1’b), 3.44 (1H, t, J4–3 = J4–5 = 9.3 Hz,
H-4), 3.53 (1H, d, J1’a–1’b = 11.9 Hz, H-1’a), 3.65–3.97 (7H, m, H-3, H-5, H-5’, H-6’a,
H-6’b, H-6a, H-6b), 4.03 (1H, t, J4’–3’ = J4’–5’ = 8.2 Hz, H-4’), 4.19 (1H, d, J3’–4’ = 8.7
Hz, H-3’), 4.61 (1H, dd, J2–1 = 3.6 Hz, J2–3 = 10.2 Hz, H-2), 5.55 (1H, d, J1–2 = 3.8
Hz, H-1). 13C NMR (75 MHz, MeOD): d 14.7 (1CH3), 26.0 (1CH2b), 24.0, 30.5, 30.8,
30.9, 31.0, 33.3 (8CH2), 35.3 (1CH2a), 62.4, 63.7 (C-6, C-6’), 63.5 (C-1’), 71.8 (C-4),
72.2 (C-5), 74.4 (C-2), 74.6 (C-3), 75.5 (C-4’), 77.7 (C-3’), 84.0 (C-5’), 91.1 (C-1),
105.9 (C-2’), 175.6 (1C = O). HRMS: m/z calcd for C24H44O12Na: 547.2730.
Found: 547.2728.
6-O-Lauroylsucrose (4c). [a]D + 45 (c 1, MeOH). Lit.[30]1H NMR (300 MHz,
MeOD): d 0.91 (3H, m, CH3), 1.31 (16H, m, (CH2)8), 1.63 (2H, m, CH2b), 2.38 (2H, m,
CH2a), 3.31 (1H, t, J4–3 = J4–5 = 9.0 Hz, H-4), 3.44 (1H, dd, J2–1 = 3.8 Hz, J2–3 = 9.8
Hz, H-2), 3.60 (1H, d, J1’a–1’b = 12.2 Hz, H-1’b), 3.65 (1H, d, J1’a–1’b = 12.2 Hz, H-1’a),
3.74 (1H, t, J3–4 = J3–2 = 9.3 Hz, H-3), 3.77–3.89 (3H, m, H-5’, H-6’a, H-6’b), 3.94–
4.08 (2H, m, H-4’, H-5), 4.11 (1H, d, J3’–4’ = 8.3 Hz, H-3’), 4.19 (1H, dd, J6a–6b = 12.0
Hz, J6b–5 = 5.4 Hz, H-6b), 4.41 (1H, dd, J6a–6b = 12.0 Hz, J6a–5 = 1.8 Hz, H-6a), 5.4
(1H, d, J1–2 = 3.8 Hz, H-1). 13C NMR (75 MHz, MeOD): d 14.7 (1CH3), 26.3 (1CH2b),
24.0, 30.5, 30.7, 30.9, 33.3 (8CH2), 35.2 (1CH2a), 64.2 (C-6’), 63.4 (C-1’), 65.0 (C-6),
71.9 (C-4), 72.2 (C-5), 73.4 (C-2), 74.7 (C-3), 76.2 (C-4’), 79.5 (C-3’), 84.1 (C-5’), 93.7
(C-1), 105.5 (C-2’), 175.8 (1C = O). HRMS: m/z calcd for C24H44O12Na: 547.2730.
Found: 547.2736.
Anal. Calcd for C24H44O12.0.8H2O: C, 53.48; H, 8.53. Found: C, 53.31; H, 8.48.
ACKNOWLEDGMENTS
Financial support from the CNRS and Be´ghin-Say is greatly acknowledged. We
thank Be´ghin-Say and l’Agence Nationale de la Recherche et de la Technologie for a
grant to VM (contrat CIFRE).
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Received March 5, 2003
Accepted July 30, 2003