Synthesis of 1,2-O-isopropylidene-3,5-O-propylidene-α-D-glucofuranose as a convenient precursor of both 6-O-alkyl and 6-O-glycidyl-D-glucose amphiphiles

Article abstract of DOI:10.1016/S0008-6215(98)00207-9

1,2-O-Isopropylidene-3,5-O-propylidene-α-D-glucofuranose (3) was synthesized by conversion of 3-O-allyl-1,2-O-isopropylidene-α-D-glucofuranose (1) into its 3-O-prop-1-enyl isomer (2), followed by rapid acid-catalysed intramolecular acetalation in an aprotic solvent. The diacetal 3 was used as the precursor of 6-O-alkyl and 6-O-glucidyl-D-glucose amphiphiles, which show thermotropic and lyotropic liquid-crystalline properties. Copyright (C) 1997 Elsevier Science Ltd.

Full text of DOI:10.1016/S0008-6215(98)00207-9

Carbohydrate Research 311 (1998) 89±94
Note
Synthesis of 1,2-O-isopropylidene-3,5-O-
propylidene-ꢀ±d-glucofuranose as a convenient
precursor of both 6-O-alkyl and
6-O-glycidyl-d-glucose amphiphiles
Laurence Vanbaelinghem, Paul Gode, Gerard Goethals, Patrick Martin,
Gino Ronco, Pierre Villa *
Â
Â
Laboratoire de Chimie Organique et Cinetique, Universite de Picardie Jules Verne, 33 rue Saint Leu,
80039 Amiens cedex, France
Received 3 December 1997; accepted 10 July 1998
Abstract
1,2-O-Isopropylidene-3,5-O-propylidene-ꢀ-d-glucofuranose (3) was synthesized by conversion
of 3-O-allyl-1,2-O-isopropylidene-ꢀ-d-glucofuranose (1) into its 3-O-prop-1-enyl isomer (2), fol-
lowed by rapid acid-catalysed intramolecular acetalation in an aprotic solvent. The diacetal 3 was
used as the precursor of 6-O-alkyl and 6-O-glucidyl-d-glucose amphiphiles, which show thermo-
tropic and lyotropic liquid-crystalline properties. # 1998 Elsevier Science Ltd. All rights reserved
Keywords: Allyl isomerisation; 1,2-O-Isopropylidene-3,5-O-propylidene-ꢀ-d±glucofuranose; 6-O-Alkyl-d-
glucose; 6-O-Glycidyl-d-glucose; CMC; Liquid crystal
Regiospeci®c derivatisation of d-glucose at C-6
requires appropriately protected intermediates.
Such conversions are readily e€ected in the fol-
lowing examples: (i) regioselective 6-O-acylation
[1,2]; (ii) substitution of 6-deoxy-6-iodo-d-glucofur-
anose to form corresponding carbamic esters and
N-alkylamines [3]. The 6-iodo intermediate fails to
give 6-O-alkyl derivatives. Such a reaction can be
achieved from 1,2-O-isopropylidene-3,5-O-aceta-
lated-ꢀ-d-glucofuranoses [4] obtained in low yield
by selective acetalation of 1,2-O-isopropylidene-ꢀ-
d-glucofuranose. Other substrates may be either
3-O-alkyl-5,6-anhydro-1,2-O-isopropylidene-ꢀ-d-
glucofuranose [5] or the methyl 2,3,4-tri-O-benzyl-
ꢀ-d-glucopyranoside [6], obtained by long multi-
step process.
We present here
a
route to 1,2-O-iso-
propylidene-3,5-O-propylidene-ꢀ-d-glucofuranose
(3) that allows all types of regiospeci®c derivatisa-
tion of d-glucose at C-6. Thus 3 was used to syn-
thesize both 6-O-alkyl and 6-O-glucidyl-d-glucoses
as new amphiphiles.
1,2-O-Isopropylidene-3,5-O-propylidene-ꢀ-d-
glucofuranose (3) was prepared from 3-O-allyl-1,2-
O-isopropylidene-ꢀ-d-glucofuranose (1) in 68%
yield following Scheme 1. The ®rst step (a)
involved isomerisation of the 3-O-allyl group to
the corresponding 3-O-prop-1-enyl group. Similar
* Corresponding author.
0008-6215/98/$Ðsee front matter # 1998 Elsevier Science Ltd. All rights reserved
PII S0008-6215(98)00207-9

90
L. Vanbaelinghem et al./Carbohydrate Research 311 (1998) 89±94
Scheme 1.
isomerisation of O-allyl derivatives has been
reported with transition metal catalysts [7] or with
potassium t-butoxide in dimethyl sulfoxide [8±11].
The latter method, applied to compound 1, gave
the ether 2 in 56% yield, whereas the yield was
80% using potassium hydroxide in toluene±dime-
thyl sulfoxide. The prop-1-enyl group in the ether 2
had the Z con®guration (JH,H 6.0 Hz). The key step
(b) was an intramolecular acetalation. In aqueous
acid solution, compound 2 gave both the diacetal 3
and 1,2-O-isopropylidene-ꢀ-d-glucofuranose (30).
It has been reported that the O-prop-1-enyl group
can be hydrolysed with 0.1 M HCl in 9:1 acetone±
water [9]. If the acid was introduced in an anhy-
drous aprotic solvent such as dichloromethane,
only the diacetal 3 was obtained (Table 1). It is
noteworthy that the intramolecular acetalation in
the aprotic solvent is rapid (5 min), even at low
acid concentration.
O-Alkylation of diacetal 3 was achieved with n-
alkyl bromide and potassium hydroxide in 4:1
toluene±dimethyl sulfoxide at room temperature to
give derivatives of type 4 in 80±97% yield
(Scheme 2). Subsequent deprotection in 9:1 tri-
¯uoroacetic acid±water at room temperature gave
the corresponding type 5 compounds (Table 2). It
is emphasized that all the samples were isolated as
pure ꢀ anomers, whereas those previously reported
[6] are ꢀ; ꢁ anomeric mixtures. Condensation of
diacetal 3 with 5,6-anhydro-3-O-n-dodecyl-1,2-
O-isopropylidene-ꢀ-d-glucofuranose [5] in the
presence of potassium hydroxide in 1:1 toluene±
ꢀ
dimethyl sulfoxide at 40 C gave the ether-linked
disaccharide 6-O-(6-deoxy-1,2-O-isopropylidene-
3,5-O-propylidene-ꢀ-d-glucofuranos-6-yl)-3-O-n-
dodecyl-1,2-O-isopropylidene-ꢀ-d-glucofuranose
(6) in 66% yield (Scheme 2). Examination of the
crude product by HPLC showed small amounts of
trisaccharide and tetrasaccharide derivatives.
Deprotection of derivative 6, using the same
conditions as used for type 4 derivatives gave 6-
O-(6-deoxy-d-glucopyranos-6-yl)-3-O-n-dodecyl-
d-glucopyranose (7) in 44% yield. NMR spectra
showed that the disaccharide 7 existed exclusively
as the pyranose form, in 3:2 ꢀ; ꢁ ratio. We expect
to apply the described reaction to alternative
substrates (3-O-alkyl-5,6-anhydro-1,2-O-isopropyl-
idene-ꢀ-d-glucofuranose, 5,6-anhydro-3-O-n-alkyl-
1,2-O-isopropylidene-ꢀ-d-galactofuranose, and
3,5-anhydro-1,2-O-isopropylidene-ꢀ-d-xylofuran-
ose) to obtain a range of 6-O-glycidyl-d-glucose
derivatives.
The amphiphilic character of 5a±d and 7 was
emphasized by a preliminary study of both the
critical micelle concentration (CMC) and the meso-
phasic transitions. 6-O-Alkyl-ꢀ-d-glucopyranoses
ꢀ
Table 1
Solvent in¯uence on the acid-catalysed intramolecular acetala-
tion of compound 2 at room temperature
(5a±d) have low CMC values in water at 25 C
(close to 5Â10 4 molL ), without signi®cant
1
change being observed upon varying the alkyl
chain length. In contrast, with the 3-O-alkyl-d-
glucose isomers [12], CMC values vary from 10.4
HCl
(M)
Solvent
Time
(min) Distributiona
3:30
Yield 3
(%)
10 4 molL for the 5b analog, to 2.3 10 4 molL
1
1
0.2
0.2
EtOH
1,4-Dioxane±water
(4:1)
120
240
20:80
20:80
18
19
for the 5d analog. However in the two series, the
surface tension (ꢂ) at these concentrations is close
0.2
0.05
0.02
CH2Cl2
CH2Cl2
CH2Cl2
5
5
5
100:0
100:0
100:0
84
85
85
1
to 28±30 mN m . All of the compounds 5a±d and
7 gave thermotropic and lyotropic liquid crystals.
In the thermotropic liquid-crystal study, we
1,2-O-isopropylidene-ꢀ-d-glucofuranose (30).
a

L. Vanbaelinghem et al./Carbohydrate Research 311 (1998) 89±94
91
Scheme 2.
observed (Table 3) that the solid±liquid-crystal
transition temperature (Tm) of the 6-O-alkyl-ꢀ-d-
glucopyranoses (5) increase upon increasing the
alkyl chain-length from n=6 to n=12 carbon
atoms (5a±5d). A similar alkyl chain-length e€ect
was noted with the 1-O-alkyl-d,l-xylitol series [13].
The disaccharidic compound 7 shows lower phase±
transition temperatures and a shorter liquid-crystal
temperature-range than the monosaccharidic com-
pound 5d, which has the same hydrophobic chain
(n±dodecyl). Moreover, for all of the mono-
saccharide compounds 5a±d the temperature of the
transitionꢀlyotropic solid±liquid crystal varies from
42 to 65 C, whereas the corresponding tempera-
ture for the disaccharide compound 7 is lower than
20 ꢀC; thꢀe isotropization temperature is always
above 95 C. In this preliminary study, lyotropic
liquid crystals are generated by water±crystal con-
tact. Control of the water concentration will allow
rationalization of these results.

92
L. Vanbaelinghem et al./Carbohydrate Research 311 (1998) 89±94
Table 2
Preparation of 6-O-alkyl-d-glucose diacetal derivatives 4a±d
and corresponding deacetalated compounds 5a±d
Surface tension, critical micelle concentration
(CMC) and phase transition determinations.ÐFor
CMC studies, an initial aqueous solution (S0) of
each compound was prepared at 25 ꢀC, corre-
sponding to the concentration C0. Several samples
were obtained by diluting S0 in the concentration
range C0:C0/2, C0/4, C0/10, C0/50, C0/100, and C0/
200. The surface tension (ꢂ) of each sample was
measured by the Wilhelmy plate method [11], after
a period of more than 1 h in the thermostated cell
O-Alkylationa
Deacetalationb
Product
Yield Product
(%)
ꢀ; ꢁ,
Yield (%)
Isolated pure
ꢀ, Yield (%)
4a
4b
4c
4d
80
96
96
97
5a
5b
5c
5d
85
82
84
81
33
41
64
73
ꢀ
a
CnH2n+1Br (1.2 equiv), KOH (2.4 equiv), 4:1 toluene±
Me2SO, RT, 3 days.
9:1 Cf3CO2H±H2O, RT, 7 h.
(25 C). The critical micelle concentration (CMC)
was determined from a plot of ꢂ ˆ fꢁlog C). The
classical slope change coordinates gave, respec-
tively, the CMC and the corresponding ꢂ values.
Phase-transition temperatures were determined
by DSC (Di€erential Scanning Calorimetry) using
a Mettler FP85 furnace and by thermal polarized-
light microscopy using an Olympus BX50 polariz-
ing transmitted light, instrument equipped with a
Mettler FP82 microfurnace. Both Mettler devices
were recorded on an FP90 central processor. For
thermotropic liquid-crystals, the transition tem-
peratures, noted Tm (solid ! liquid crystal) and
Ti (liquid crystal ! isotropic liquid) are Tonset
b
1. Experimental
General methods.ÐMelting points were deter-
mined on an electrothermal automatic apparatus,
and are uncorrected. Optical rotations, for solutions
in CHCl3 or MeOH, were measured with a digital
polarimeter JASCO model DIP-370 at 25 ꢀC.
NMR spectra were recorded with a Bruker WB-
300 instrument for solutions in CDCl3 or
Me2SO-d6 (internal Me4Si). Elemental analyses
were performed by the Service Central de Micro-
Analyse du Centre National de la Recherche Sci-
enti®que (Vernaison, France). Reactions were
monitored by either HPLC (Waters 721), using
either the reverse-phase columns RP-18 (Merck) or
PN 27-196 (Waters), or CPG (Girdel) with either
the columns OV 17 or SE 30. Column chromato-
graphy was performed on silica gel (60 mesh,
Matrex) by gradient elution with hexane±acetone
(in each case the ratio of silica gel to product mix-
ture to be puri®ed, was 30:1).
ꢀ
1
measured at 2 C min by DSC. For lyotropic
liquid-crystals, transition temperatures were deter-
mined by simply allowing crystals of the test
material to dissolve in water, thereby creating a
concentration gradient which supports mesophase
formation.
1,2-O-Isopropylidene-3-O-prop-1-enyl-a-d-gluco-
furanose (2).ÐTo a solution of 3-O-allyl-1,2-O-
isopropylidene-ꢀ-d-glucofuranose (1) [5] (40 g,
1
154 mmol) in 1:1 toluene±Me2SO (200 g L ) was
added powdered KOH (34.5 g, 616 mmol). After
ꢀ
4 h at 100 C, the mixture was ®ltered and water
was added. The organic phase was separated, dried
(Na2SO4) and concentrated under diminished
pressure. 1,2-O-Isopropylidene-3-O-prop-1-enyl-ꢀ-
d-glucofuranose (2) was isolated after puri®cation
by column chromatography with 4:1 hexane±ace-
tone (32 g, 80%): mp 67±68 ꢀC; [ꢀ]d24 +17.3 ꢀ (c 1.0,
CHCl3); 13C NMR (CDCl3): ꢃ143.7 (C-ꢀ); 111.9
(C-iso), 105.0 (C-1), 103.6 (C-ꢁ), 83.5, 82.7, 79.9
(C-2, C-3, C-4), 68.8 (C-5), 64.3 (C-6), 26.1 and
26.6 (CH3-iso), 9.1 (C-ꢂ). 1H NMR (CDCl3): ꢃ6.00
(dq, 1 H, H-ꢁ), 5.88 (d, 1 H, J1±2 3.7 Hz, H 1),
4.51 (2d, 2 H, J2±3 0 Hz, H-2 and H ꢀ), 4.24 (d, 1
H, J3,4 2.9 Hz, H-3), 4.12 (dd, 1 H, J4,5 8.5 Hz, H-4),
3.90 (m, 1 H, J5±6b 5.1 Hz, H-5), 3.80 (dd, 1 H, J6a±6b
9.0 Hz, H-6), 3.69 (dd, 1 H, H-6b), 1.50 (d, 3 H,
H-ꢂ), 1.45 and 1.26 (2s, CH3-iso). Anal. Calcd for
Table 3
Thermotropic phase-transition temperatures (ꢀC) for 6-O-
alkyl-ꢀ-d-glucopyranoses (5a±d) and 6-O-glucidyl-d-glucopyr-
anoses (7)
Product
Microscopy
Tmb ( )d Tic ( )d
65.5 129.2
DSCa
Tic ( )d
127.6
Tmb ( )d
59.3
5a
5b
5c
5d
7
78.2 (83.0) 148.0 (153.0) 76.0 (89.2) 145.8 (160.5)
82.0 (84.0) 146.3 (155.0) 82.0
95.5 (93.0) 137.3 (163.0) 91.0
148.0
131.4
121.8
Ð
Ð
87.1
a
ꢀ
1
Measured at 2 C min
Melting temperature (solid±liquid crystal transition).
Isotropization temperature (liquid crystal±isotropic liquid
.
b
c
transition).
d
Literature data, for ꢀ; ꢁ anomer mixtures [6].

L. Vanbaelinghem et al./Carbohydrate Research 311 (1998) 89±94
93
C12H20O6 (260.86): C, 55.25; H, 7.73. Found: C,
55.19; H, 7.78.
glucofuranose (4) was isolated after puri®cation by
column chromatography with 49:1 hexane±acetone
(Table 4). 13C NMR (CDCl3): ꢃ 111.9 (C-iso), 104.7
1,2-O-Isopropylidene-3,5-O-propylidene-a-d-gluco-
furanose (3).ÐTo a solution of 2 (10 g, 38.5 mmol)
(C-1), 96.7 (C-ꢀ), 84.0 (C-2), 77.5 (C-4), 73.5 (C-3),
0
1
0
in CH2Cl2 (100 g L ) was added dropwise 1.8 mL
72.1 (C-5, C-6), 71.6 (C-ꢀ ), 31.8 to 22.0 (CH2 and
of 36 M HCl. After 5 min at room temperature, the
mixture was neutralized with satd aq NH4Cl. The
organic phase was separated, washed with water
(twice), dried (Na2SO4) and concentrated under
diminished pressure. 1,2-O-Isopropylidene-3,5-O-
propylidene-ꢀ-d-glucofuranose (3) was isolated by
crystallization of the crude product from ꢀ3:7 die-
thylether±hexane (8.5 g, 85%); mp 98±102 C; [ꢀ]d24
+12.1ꢀ(c 1.3, CHCl3); 13C NMR (CDCl3): ꢃ 111.7
(C-iso), 104.8 (C-1), 95.3 (C-ꢀ), 83.8, 77.2, 73.3 (C-
2, C-3, C-4), 72.7 (C-5), 61.2 (C-6), 27.7 (C-ꢁ), 26.0
and 26.6 (CH3-iso), 8.0 (C-ꢂ). 1H NMR (CDCl3): ꢃ
5.95 (d, 1 H, J1±2 3.7 Hz, H-1), 4.70 (t, 1 H, H-ꢀ),
4.52 (d, 1 H, J2±3 0 Hz, H-2), 4.18 (d, 1 H, J3±4
2.1 Hz, H-3), 4.17 (dd, 1 H, J4±5 2.1 Hz, H-4), 3.90
(m, 1 H, J5±6a 3.2 Hz, J5±6b 4.9 Hz, H-5), 3.75 (dd, 1
H, J6a±6b 11.9 Hz, H-6a), 3.71 (dd, 1 H, H-6b), 1.57
(dq, 2 H, H-ꢁ), 1.45 and 1.26 (2s, CH3-iso), 0.88 (t,
3 H, H-ꢂ). Anal. Calcd for C12H20O6 (260.86): C,
55.25; H, 7.73. Found: C, 55.32; H, 7.68.
C-ꢁ), 26.0 and 26.6 (CH3-iso), 14.0 (C-!0), 8.0 (C-ꢂ).
1H NMR (CDCl3): ꢃ 5.95 (d, 1 H, J1±2 3.7 Hz, H-1),
4.85 (t, 1 H, Jꢀ;ꢁ 5.2 Hz, H-ꢀ), 4.50 (d, 1 H, J2±3 0 Hz,
H-2), 4.23 (d, 1 H, J3±4 1.9 Hz, H-3), 4.16 (m, 1 H, J5±
6b 4.5 Hz, H-5), 4.03 (m, 1 H, J4±5 1.2 Hz, H-4), 3.71
(dd, 1 H, J5±6a 4.2 Hz, H-6a), 3.62 (dd, 1 H, J6a±6b
10.4 Hz, H-6b), 3.38 (t, 2 H, H-ꢀ0, H-ꢀ00), 1.21!1.54
(CH2chain, CH3-iso), 0.83 (CH3-!0, CH3-ꢂ).
6-O-Alkyl-a-d-glucopyranose (5).Ð6-O-Alkyl-
1,2-O-isopropylidene-3,5±O-propylidene-ꢀ-d-gluco-
furanose (4) (2 g) were added to a stirred solution
1
of 9:1 CF3COOH±H2O (100 g L ). After 7 h at
room temperature, the solution was concentrated
to dryness under diminished pressure. The desired
products were crystallized from diethyl ether
(Table 4). NMR showed that only the ꢀ pyranose
form crystallized. 13C NMR (CDCl3): ꢃ 94.1 (C-1),
75.9 (C-3), 74.9 (C-2), 72.9 (C-4), 72.7 (C-5), 72.4
(C-6), 72.2 (C-ꢀ0), 32.1 ! 22.9 (CH2chain), 14.3 (C-!0).
1H NMR (CDCl3): ꢃ 5.88 (d, 1 H, J1±2 3.6 Hz, H-1),
4.83 (m, 1 H, H-5), 4.72 (dd, 1 H, J3±4 9.1 Hz, H-3),
4.26 (m, 1 H, J5±6b 2.0 Hz, H-6b), 4.20 (dd, 1 H, J2±3
9.5 Hz, H-2), 4.12 (dd, 1 H, J4±5 9.4 Hz, H-4), 4.07 (m,
1 H, J6a±6b 10.3 Hz, H-6a), 3.60 (m, 2 H, H-ꢀ0, H-ꢀ00),
1.21 ! 1.64 (CH2chain), 0.83 (CH3-!0).
6-O-Alkyl-1,2-O-isopropylidene-3,5-O-propyl-
idene-a-d-glucofuranose (4).ÐTo a solution of 3
(10 g, 38.5 mmol) and 1.2 equiv of CnH2n+1Br
1
(n=6, 8, 10, 12) in 4:1 toluene±Me2SO (100 g L )
was added powdered KOH (5.2 g, 92.3 mmol).
After 3 days at room temperature, the mixture was
®ltered and the ®ltrate neutralized with satd aq
NH4Cl. The organic phase was separated, washed
with water (twice), dried (Na2SO4) and con-
centrated under diminished pressure. The 6-O-
alkyl-1,2-O-isopropylidene-3,5-O-propylidene-ꢀ-d-
6-O-(6-Deoxy-1,2-O-isopropylidene-3,5-O-propyl-
idene-a-d-glucofuranos-6-yl)-3-O-n-dodecyl-1,2-O-
isopropylidene-a-d-glucofuranose (6).ÐTo a solu-
tion of 3 (2.4 g, 9 mmol) and 3-O-dodecyl-5,6-
anhydro-1,2-O-isopropylidene-ꢀ-d-glucofuranose
1
[5] (1.1 g, 3 mmol) in 1:1 toluene±Me2SO (100 g L )
Table 4
Physicochemical and microanalytical data for compounds 4a±d and 5a±d
Calcd
Found
Product
Yield (%)
Mpa (ꢀC)
[ꢀ]2d5
Formula
C
H
C
H
4a
4b
4c
4d
5a
5b
5c
5d
80
96
96
97
33
41
64
73
Oil
Oil
Oil
Oil
65.5
78.2
82.0
95.5
6.8ꢀ (c 1.4)b
6.4ꢀ (c 1.2)b
5.0ꢀ (c 1.2)b
3.5ꢀ (c 1.3)b
49.30ꢀ (c 1.3)c
45.9ꢀ (c 1.2)c
41.8ꢀ (c 1.2)c
37.4ꢀ (c 1.0)c
C18H32O6 (344.45)
C20H36O6 (372.50)
C22H40O6 (400.55)
C24H44O6 (428.6 1)
C12H24O6 (264.32)
C14H28O6 (292.37)
C16H32O6 (320.42)
C18H36O6 (348.48)
62.77
64.49
9.36 62.63
9.74 64.55
9.42
9.82
65.97 10.07 66.11 10.12
67.26 10.35 67.15 10.41
54.53
57.51
59.98 10.07 60.09 10.12
62.04 10.41 61.95 10.38
9.15 54.64
9.65 57.59
9.21
9.71
a
Measured by thermal microscopy.
In CHCl3.
in MeOH (stabilized during 5 days).
b
c

94
L. Vanbaelinghem et al./Carbohydrate Research 311 (1998) 89±94
was added powdered KOH (0.56 g, 10 mmol).
ꢀ
Acknowledgements
After 40 h at 40 C, the mixture was ®ltered and
The authors thank the Conseil Regional de
Picardie, the Centre de Valorisation des Glucides
and the Ministere de la Recherche for ®nancial
support. We thank Professor G. Mackenzie for his
critical comments.
the ®ltrate neutralized with satd aq NH4Cl. The
organic phase was separated, washed with water
(twice), dried (Na2SO4) and concentrated under
diminished pressure. The 6-O-(6-deoxy-1,2-O-iso-
propylidene-3,5-O-propylidene-ꢀ-d-glucofuranos-
6-yl)-3-O-n-dodecyl-1,2-O-isopropylidene-ꢀ-d-glu-
cofuranose (6) was isolated after puri®cation by
column chromatography with 4:1 hexane±acetone
(1.25 g, 66%): [ꢀ]2d4 15.7 ꢀ (c 1.0, CHCl3); 13C
NMR (CDCl3): ꢃ 111.6 (C-iso), 105.0 (C-1), 104.8
(C-10), 96.4 (C-ꢀ0), 83.9 (C-20), 82.6 (C-3), 82.1 (C-
2), 79.5 (C-4), 77.3 (C-40), 73.5 (C-6), 73.2 (C-30),
71.9 (C-50, C-60), 70.6 (C-ꢀchain-), 68.0 (C-5), 31.8
to 22.6 (CH2chain and C-ꢁ0), 26.0 to 26.7 (CH3-iso),
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14.0 (C-!chain), 7.9 (C-ꢂ0). H NMR (CDCl3):
1
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ꢃ 5.93 (d, 1 H, J1±2 3.7 Hz, H-10), 5.83 (d, 1 H, J1±2
3.7 Hz, H-1), 4.74 (m, 1 H, H-ꢀ0), 4.49 (1 H, H-20),
4.48 (1 H, H-2), 4.21 (1 H, H-50), 4.19 (1 H, H-40),
4.03 (2 H, H-4, H-5), 3.98 (1 H, H-30), 3.89 (1 H,
H-3), 3.75 (2 H, H-60), 3.63 (2 H, H-6), 3.59 and 3.44
(2 H, H-ꢀ), 1.56 to 1.20 (21 H, H-ꢁ0 and chain),
1.42 (d, 3 H, H-ꢂ0), 1.26 and 1.20 (4s, CH3-iso),
0.83 (3 H,C-!). Anal. Calcd for C33H58O11 (630.0):
C, 62.86; H, 9.21. Found: C, 63.08; H, 9.27.
6-O-(6-Deoxy-d-glucopyranos-6-yl)-3-O-dodecyl-
d-glucopyranose (7).ÐThis material was prepared
from the ether-linked 6 (1.35 g, 2.14 mmol) using
the same deprotection method as for the type 4
compound, but dring 25 min instead of 7 h (0.48 g,
ꢀ
44); mp 87.1 C. On account of the complexity of
the NMR spectra, only chemical shifts of C-1 and
C-3 are given; 98.8 (C-1ꢁ), 94.0 (C-1ꢀ), 87.1
(C-3ꢁ), 84.2 (C-3ꢀ). Anal. Calcd for C24H46O11
(510.0): C, 56.47; H, 9.02. Found: C, 56.29; H,
9.15.