Bis-desulfoglucosinolates: A new class of bolaforms

Article abstract of DOI:10.1081/SCC-120012980

Bis-desulfoglucosinolates 14-18 bearing D-gluco, lacto, malto and cellobio saccharidic moieties were synthesized in two steps from the corresponding protected 1-thio-β-D-glycopyranoses 5, 8, 10 and 12 and bis-hydroximoyl chlorides 3a and 4a derived from 1,8-octanedial (1) and 1,12-dodecanedial (2). Fully deprotections of the intermediate O-acetylated derivatives 6, 7, 9, 11 and 13 were realized either using Zemplen method or methanol/triethylamine/water mixture, the choice of the conditions being dependent on the solubility in methanol of the fully and partially acetylated derivatives.

Full text of DOI:10.1081/SCC-120012980

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BIS-DESULFOGLUCOSINOLATES: A NEW CLASS OF
BOLAFORMS
Dominique Lafont a , Yves Chevalier b , Valérie Grumel c , Stéphanie Cassel c & Patrick Rollin
c
a Laboratoire de Chimie Organique II , Université Lyon I , UMR 5622 CNRS, Bât 308, 43 Bd du
11 Novembre 1918, Villeurbanne Cedex, 69622, France
b Laboratoire des Matériaux Organiques à Propriétés Spécifiques , UPR 9031 CNRS,
Vernaison, 69390, France
c ICOA , Université d'Orléans , UPRES-A 6005, B.P. 6759, Orléans Cedex 2, F-45067, France
Published online: 16 Aug 2006.
To cite this article: Dominique Lafont , Yves Chevalier , Valérie Grumel , Stéphanie Cassel & Patrick Rollin (2002) BIS-
DESULFOGLUCOSINOLATES: A NEW CLASS OF BOLAFORMS, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:19, 2919-2930, DOI: 10.1081/SCC-120012980
To link to this article: http://dx.doi.org/10.1081/SCC-120012980
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 19, pp. 2919–2930, 2002
BIS-DESULFOGLUCOSINOLATES:
A NEW CLASS OF BOLAFORMS
2
3
Dominique Lafont,1, Yves Chevalier, Valerie Grumel,
*
Stephanie Cassel,3 and Patrick Rollin3
1Laboratoire de Chimie Organique II, UMR 5622
CNRS, Universite Lyon I, Bat 308, 43 Bd du 11
Novembre 1918, 69622 Villeurbanne Cedex, France
2Laboratoire des Materiaux Organiques a Proprietes
Specifiques, UPR 9031 CNRS, 69390 Vernaison, France
3ICOA, UPRES-A 6005, Universite d’Orleans,
B.P. 6759, F-45067 Orleans Cedex 2, France
ABSTRACT
Bis-desulfoglucosinolates 14–18 bearing D-gluco, lacto, malto
and cellobio saccharidic moieties were synthesized in two steps
from the corresponding protected 1-thio-b-D-glycopyranoses
5, 8, 10 and 12 and bis-hydroximoyl chlorides 3a and 4a
derived from 1,8-octanedial (1) and 1,12-dodecanedial (2).
Fully deprotections of the intermediate O-acetylated deriva-
tives 6, 7, 9, 11 and 13 were realized either using Zemplen
method or methanol/triethylamine/water mixture, the choice
of the conditions being dependent on the solubility in metha-
nol of the fully and partially acetylated derivatives.
Key Words: Desulfoglucosinolates; Bolaforms; Amphiphiles
*Corresponding author. E-mail: lafont@univ-lyon1.fr
2919
DOI: 10.1081/SCC-120012980
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2920
LAFONT ET AL.
INTRODUCTION
Bolaamphiphiles are molecules in which hydrophilic groups are
connected on both ends of a hydrophobic bridging chain.[1–4] The interest
for these substances has increased for synthetic, biological and practical
points of view.[5–7] Natural bolaamphiphilic structures are encountered in
membranes of thermophilic Archaebacteria.[8] The structure confers a very
high stability to the membrane under extreme environmental conditions.
Non-ionic bolaamphiphilic surfactants having sugars at one[9] or
both[10–16] ends have been synthesized, because of: (1) their ability to from
vesicles and supramolecular arrangements and (2) their potential applica-
tions in the biomedical and pharmaceutical fields. Some years ago, D-glucos-
aminyl bolaamphiphiles were prepared in the laboratory and their
surfactant properties in water solution were described.[17]
Glucosinolates constitute a structurally homogeneous family of over
110 naturally-occurring anomeric esters—thiohydroximates—derived from
1-thio-b-D-glucose. They can undergo smooth enzymatic desulfatation by
sulfatase (EC 3.1.6.1) to produce the corresponding desulfoglucosinolates,
which have major analytical applications.[18]
The synthesis of natural and artificial non-sulfated glucosinolates is
well-documented.[19] We herein report the synthesis and applications of
bolaamphiphilic derivatives designed a bis-desulfoglucosinolate template.
RESULTS AND DISCUSSION
Synthetic pathway to bolaamphiphilic glucosinolates involved the
preparation of the dioximes 3 and 4, which were further condensed with
1-thiosugar derivatives. Thus, 1,8-octanedial 1 and 1,12-dodecanedial 2 were
synthesized from commercially available 1,8-octanediol and 1,12-dodecane-
diol, respectively. In a first attempt, the corresponding ditosylates (obtained
from the diols in 75% yield) were heated at 155ꢀC in DMSO, in the presence
of sodium carbonate as described by Stirling et al.[20] However, the purifica-
tion of dialdehydes proved tedious due to the presence of side-products and

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BIS-DESULFOGLUCOSINOLATES
2921
the overall yields could never exceed 40%. In contrast, when using o-iodoxy-
benzoic acid (IBX) in DMSO,[21,22] direct oxidation of the diols led to 1 and
2 in high yields. Reacting the dialdehydes with hydroxylamine hydro-
chloride in the presence of sodium acetate afforded the dioximes 3 and 4
in quantitative yields.
The dioximes were then transformed into the bis-hydroximoyl chlo-
rides 3a and 4a, through chlorination with N-chlorosuccinimide in DMF.
The key-step in the synthesis of bis-desulfoglucosinolates was the stereo-
specific 1,3-addition of the protected saccharidic thiols on the transient
bis-nitrile oxides produced in situ by basic treatment of 3a and 4a. Thus,
coupling reactions led to symmetrical bolaforms in the D-gluco 6,7, lacto 9,
malto 11 and cellobio 13 series starting from the known b-D-glycosyl
mercaptans 5,8,10 and 12, in yields ranging from 57 to 86%. O-
Deacetylation of these precursors was effected either using Zemplen
method or the MeOH/NEt3/H2O mixture, the choice of the conditions
being dependent on the solubility in MeOH of the fully or partially acety-
lated derivatives.
In the case of the condensation of 2,3,4,6-tetra-O-acetyl-1-thio-b-D-
glucopyranose 5 with the C-8 bis-hydroximoyl chloride 3a, the main impur-
ity was identified as the unsymmetrical a,b-derivative 6a; this could be
due to the presence of some a-thiol in the starting material 5. The structure
of 6a was ascertained from 1H NMR spectrum (ꢀH-1b ¼ 5.05 ppm,
ꢀH-1a ¼ 6.23 ppm, J1,2 ¼ 5.6 Hz); the large value for J1,2 has already been
observed for artificial a-glucosinolates.[23]
Evidence for the b-configuration of all the peracetylated and depro-
tected derivatives resulted from the chemical shifts for H-1 and the J1,2
1
coupling in H-NMR spectra.
Surface tension properties of these derivatives were performed in
aqueous solutions. Thus, critical micellar concentration (cmc) was carried
out for water-soluble compounds above the Krafft temperature by the
Lecomte du Nouy ring method.[24] However monosaccharidic (14,15) and
disaccharidic (16,18) bolaforms were not soluble enough in water to allow
measurement. In contrast, due to its high water-solubility, the malto deriva-
tive 17 gave 60 mmol/L for the cmc at 25ꢀC and the area per molecule at the
air–water interface was found to be 52 A2/molecule; the small value of the
area would imply a tight packing of the disaccharidic headgroups at
the air–water interface. Intermolecular hydrogen bonding can be proposed
as the origin.[25] In the sugar-based bolaform surfactant series, the cmc
of bolaform D-glucosaminyl surfactants were in the range 70–80 mmol/L,
independent of the arm length and temperature;[17] these values for
the glucosamine headgroup are close to the value measured for the malto
derivative.

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2922
LAFONT ET AL.
CONCLUSION
A new class of bolaamphiphilic desulfoglucosinolates has been pre-
pared in a few steps and in good yields. However, such compounds
showed low water solubilities; O-sulfatation of both thiohydroximate func-
tions of compounds 14–18 certainly would help to overcome that difficulty.
EXPERIMENTAL
General methods: DMF was dried on 4 A molecular sieves followed
by distillation under reduced pressure. Methanol was refluxed over
magnesium before distillation. Melting points were determined on a
Buchi apparatus and were uncorrected. TLC analyses were performed

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BIS-DESULFOGLUCOSINOLATES
2923
on aluminium sheets coated with silica gel 60 F 254 Merck. Compounds
were visualized by spraying the TLC plates with dilute 15% aqueous
sulfuric acid, followed by charring at 150ꢀC for a few minutes. Column
chromatography was performed on silica-gel Geduran Si 60 Merck.
Optical rotations were recorded on a Perkin Elmer 241 polarimeter in a
1 dm cell at 21ꢀC. H and 13C NMR spectra were recorded with Bruker
1
AC-200 or AM-300 spectrometers operating at 200 or 300 MHz and 50 or
75.5 MHz, respectively with tetramethylsilane as internal standard.
Elemental analyses were carried out by the Service Central d’Analyses
du CNRS (Vernaison, France).
1,8-Octanedial (1): To a solution of o-iodobenzoic acid[21,22] (7.30 g,
29.43 mmol) in DMSO (30 mL), 1,8-octanediol (1.62 g, 11.08 mmol) was added
and stirring was maintained for four hours. Work-up was performed by dilution
with water (150 mL), filtration of the precipitate and extraction of the reaction
mixture with Et2O (3 Â 75 mL). The combined organic layers were dried
(Na2SO4) and concentrated under reduced pressure to afford the crude product
which was purified by column chromatography with EtOAc/petroleum ether
(1 : 1 v/v) as the eluent. Compound 1: 1.36 g (87% yield); liquid; Rf 0.76
(EtOAc/petroleum ether 1 : 1 v/v); 1H NMR (CDCl3) ꢀ 1.28 (m, 4H, 2CH2),
1.59 (m, 4H, 2CH2), 2.42 (dt, 4H, J ¼ 3.6 Hz, J ¼ 1.8 Hz, 2CH2CHO), 9.76 (t,
2H, J ¼ 1.8 Hz, 2CHO) was similar to the literature.[26]
1,12-Dodecanedial (2): Prepared as described above from 1,12-dodeca-
nediol (2.02 g, 10 mmol). The crude product was purified by column chro-
matography with EtOAc/petroleum ether (1 : 2 v/v) as the eluent.
Compound 2: 1.83 g (92% yield); liquid; Rf 0.66 (EtOAc/petroleum ether
1
1 : 2 v/v); H NMR (CDCl3) ꢀ 1.28 (m, 12H, 6CH2), 1.59 (m, 4H, 2CH2),
2.42 (dt, 4H, J ¼ 3.6 Hz, J ¼ 1.8 Hz, 2CH2CHO), 9.76 (t, 2H, J ¼ 1.78 Hz,
2CHO) was similar to the literature.[27]
1,8-Octanedial dioxime (3): 1,8-Octanedial (1) (1.35 g, 9.50 mmol) was
added to a solution of hydroxylamine hydrochloride (3.96 g, 57.0 mmol) and
sodium acetate trihydrate (7.76 g, 57.0 mmol) in water (42 mL). After addi-
tion of ethanol (250 mL), the solution was stirred for 3 h. Concentration
of the solution to 40 mL afforded an insoluble solid which was recovered
by filtration, washed with water (10 mL), then with ethanol (5 mL) and with
hexane (5 mL). Compound 3: 1.47 g (90% yield); solid, m.p. 152–153ꢀC
(lit.[28] m.p. 155–156ꢀC); 1H NMR (CD3SOCD3) ꢀ 1.28–1.43 (m, 8H,
4CH2), 2.00–2.25 (m, 4H, 2CH2CH¼NOH), 6.63 (t, 2H, J ¼ 5.4 Hz,
2CH¼NOH Z isomer 93%), 7.29 (t, 2H, J ¼ 5.9 Hz, 2CH¼NOH E
isomer 7%), 10.35 (s, 2H, 2CH¼NOH E isomer 7%), 10.72 (s, 2H,
2CH¼NOH Z isomer 93%).
1,12-Dodecanedial dioxime (4): 1,12-Dodecanedial (2) (0.870 g,
4.39 mmol) was treated as described above. Compound 4: 0.840 g (84%

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2924
LAFONT ET AL.
yield); solid, m.p. 151ꢀC (lit.[29] m.p. 137–139ꢀC); H NMR (CD3SOCD3) ꢀ
1.28–1.43 (m, 16H, 8CH2), 2.10–2.25 (m, 4H, 2CH2CH¼NOH), 6.62 (t, 2H,
J ¼ 4.9 Hz, 2CH¼NOH Z isomer 93%), 7.28 (t, 2H, J ¼ 5.5 Hz, 2CH¼NOH
E isomer 7%), 10.34 (s, 2H, 2CH¼NOH E isomer 7%), 10.71 (s, 2H,
2CH¼NOH Z isomer 93%).
1
General procedure for the synthesis of bis-[(Z )-1-(S )-b-D-glycopyrano-
syl] 1,n-alkanebis-thiohydroximate: The dioxime 3 or 4 (1.0 mmol) was added
to a flask containing DMF (15 mL), and a few drops of pyridine; N-chlor-
osuccinimide (0.198 g, 2.0 mmol) was slowly added and the reaction mixture
was stirred at r.t. for two days. After addition of the 1-thio-b-D-glycopyr-
anose derivative (5, 8, 10 or 12) (1.0 mmol), triethylamine (418 mL, 3.0 mmol,
3 eq.) was added dropwise. The mixture was stirred 2 h more, and concen-
trated. The residue was extracted with CH2Cl2, the organic phase washed
with water, dried (MgSO4) and concentrated again. The residue was purified
by column chromatography.
Bis-[2,3,4,6-tetra-O-acetyl-1-(S )-b-
thiohydroximate (6) and [(2,3,4,6-tetra-O-acetyl-1-(S )-b-
(2,3,4,6-tetra-O-acetyl-1-(S )-a-
(6a): Obtained as described above from 2,3,4,6-tetra-O-acetyl-1-thio-b-
D
-glucopyranosyl]
1,8-octanebis-
-glucopyranosyl)
D
D
-glucopyranosyl)] 1,8-octanebisthiohydroximate
-glu-
D
copyranose (5) and the dioxime 3. The product recovered after purification by
column chromatography (EtOAc/petroleum ether (1 : 1 À >2 : 1 v/v) still
showed the presence of a side-product which was completely eliminated by
solid–liquid extraction with Et2O; the insoluble fraction was pure 6 and the
soluble fraction (mixture 6a/6) was then purified again by column chromato-
graphy (Et2O/EtOAc 13 : 1 v/v). Product 6a: (0.027 g, 3% yield) was an amor-
phous solid; Rf 0.50 (EtOAc/petroleum ether 2 : 1 v/v), Rf 0.44 (EtOAc/Et2O
1 : 13 v/v); [ꢁ]D 0ꢀ (c, 1.0, CHCl3); 1H NMR (CDCl3) ꢀ 1.42 (m, 4H, 2CH2), 1.67
(m, 4H, 2CH2), 2.03, 2.05, 2.06, 2.07, 2.08, 2.09, 2.12, 2.13 (8s, 24H,
8CH3COO), 2.58 (m, 4H, 2CH2C¼NOH), 3.81 (ddd, 1H, J4,5 ¼ 10.1 Hz
J5.6a ¼ 2.3 Hz, J5,6b ¼ 5.3 Hz, H-5b), 4.09 (dd, 1H, J5,6b ¼ 2.0 Hz,
J6a,6b ¼ 12.2 Hz, H-6ba), 4.18 (dd, 1H, J6a,6b ¼ 12.3 Hz, H-6bb), 4.23 (dd, 1H,
H-6ab), 4.32 (dd, 1H, J5,6a ¼ 4.2 Hz, H-6aa), 4.45 (ddd, 1H, J4,5 ¼ 10.0 Hz, H-
5a), 5.07–5.17 (m, 5H, H-1b,2a,2b,4a,4b), 5.32 (dd, 1H, J2,3 ¼ 8.8 Hz,
J3,4 ¼ 9.2 Hz, H-3b), 5.46 (dd, 1H, J2,3 ¼ 10.0 Hz, J3,4 ¼ 9.6 Hz, H-3a), 6.23 (d,
1H, J1,2 ¼ 5.9 Hz, H-1a), 8.85 and 8.92 (s, 2H, 2C¼NOH). Product 6 (0.646 g,
72% yield) was a solid; m.p. 208ꢀC; Rf 0.50 (EtOAc/petroleum ether 2 : 1 v/v),
Rf 0.37 (EtOAc/Et2O 1/13 v/v); [ꢁ]D À 16ꢀ (c, 1.0, CHCl3); H NMR (CDCl3)
1
ꢀ 1.42 (m, 4H, 2CH2), 1.67 (m, 4H, 2CH2), 2.03, 2.05, 2.06, 2.09 (4s, 24H,
8CH3COO), 2.58 (m, 4H, 2 CH2C¼NOH), 3.81 (ddd, 2H, J4,5 ¼ 10.0 Hz,
J5,6a ¼ 2.3 Hz, J5,6b ¼ 5.3 Hz, 2H-5), 4.18 (dd, 2H, J6a,6b ¼ 12.3 Hz, 2H-6b),
4.23 (dd, 2H, 2H-6a), 5.03–5.10 (m, 4H, 2H-1,2), 5.12 (dd, 2H, J3,4 ¼ 9.5 Hz,
2H-4), 5.26–5.34 (m, 2H, 2H-3), 8.28 (s, 2H, 2C¼NOH).

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BIS-DESULFOGLUCOSINOLATES
2925
Anal. Calcd. for C36H52N2O20S2 (896.92): C, 48.20; H, 5.84; N, 3.12.
Found: C, 48.48; H, 5.98; N, 3.33.
Bis-[2,3,4,6-tetra-O-acetyl-1-(S )-b-D-glucopyranosyl] 1,12-dodecane-
bisthiohydroximate (7): Obtained in 75% yield as described above from
2,3,4,6-tetra-O-acetyl-1-thio-b-D-glucopyranose (5) and the dioxime 4. The
pure product was recovered after purification by column chromatog-
raphy (EtOAc/petroleum ether (1 : 1 v/v). Product 7: solid, m.p. 165ꢀC;
Rf 0.60 (EtOAc/petroleum ether 1 : 1 v/v); [ꢁ]D À14ꢀ (c, 1.0, CHCl3);
1H NMR was identical to the one obtained for the compound 6 except ꢀ
1.42 (m, 12H, 6CH2).
Anal. Calcd for C40H60N2O20S2 (953.022): C, 50.41; H, 6.35; N, 2.94.
Found: C, 50.27; H, 6.18; N, 2.83.
Bis-[4-O-(2,3,4,6-tetra-O-acetyl-b-
D
-galactopyranosyl)-2,3,6-tri-O-acetyl-1-
-glucopyranosyl]1,8-octanebisthiohydroximate(9): Obtained as described
from 4-O-(2,3,4,6-tetra-O-acetyl-b- -galactopyranosyl)-2,3,6-tri-O-
-glucopyranose (8) and the dioxime 3. The pure product 9
(S )-b-D
above
D
acetyl-1-thio-b-
D
was recovered after purification by column chromatography (EtOAc/petroleum
ether (7 : 2 v/v). Product 9 (1.237 g, 84% yield) was a solid; m.p. 225ꢀC, Rf 0.48
(EtOAc/petroleum ether 7 : 2 v/v); [ꢁ]D À 23ꢀ (c, 1.0, CHCl3); 1H NMR (CDCl3)
ꢀ 1.40 (m, 2H, 2CH2), 1.64 (m, 4H, 2CH2), 1.99, 2.04, 2.06, 2.10, 2.10, 2.11, 2.15
(7s, 42H, 14CH3COO), 2.49 (m, 4H, 2CH2C¼NOH), 3.69 (ddd, 2H,
J4,5 ¼ 9.5 Hz, J5,6a ¼ 1.6 Hz, J5,6b ¼ 6.0 Hz, 2H-5), 3.82 (dd, 2H, J3,4 ¼ 8.7 Hz,
2H-4), 3.88 (ddd, 2H, J4 ,5 ¼ 0.5 Hz, J5 ,6 a ¼ 6.5 Hz, J5 ,6 b ¼ 6.5 Hz, 2H-50),
0
0
0
0
0
0
4.03–4.14 (m, 6H, 2H-6b,60a,60b), 4.45 (dd, 2H, J6a,6b ¼ 12.4 Hz, 2H-6a), 4.48
0
0
0
(d, 2H, J1 ,2 ¼ 7.7 Hz, 2H-1 ), 4.95 (dd, 2H, J1,2 ¼ 8.0 Hz, J2,3 ¼ 8.5 Hz, 2H-2),
0
0
0
0
0
4.96 (dd, 2H, J2 ,3 ¼ 10.4 Hz, J3 ,4 ¼ 3.3 Hz, 2H-3 ), 4.97 (d, 2H, 2H-1), 5.09 (dd,
2H, 2H-20), 5.25 (dd. 2H, 2H-3), 5.34 (dd, 2H, 2H-40), 8.28 (s, 2H, 2C¼NOH);
13C NMR (CDCl3)
ꢀ 20.90, 21.05, 21.05, 21.05, 21.08, 21.18, 21.24
(14C, 14CH3COO), 27.09, 28.60, 32.44 (6CH2), 61.19 (2C, 2C-60), 62.75 (2C,
2C-6), 66.99 (2C, 2C-40), 69.51 (2C, 2C-20), 70.78 (2C, 2C-2), 71.13 (2C, 2C-
50), 71.31 (2C, 2C-30), 74.22 (2C, 2C-3), 76.37 (2C, 2C-4), 76.86 (2C, 2C-5),
81.06 (2C, 2C-1), 101.53 (2C, 2C-10), 152.55 (2C, 2C¼NOH), 169.73, 169.6,
170.33, 170.49, 170.57, 170.81, 170.90 (14C, 14CH3COO).
Anal. Calcd. for C60H84N2O36S2 (1473.42): C, 48.90; H, 5.75; N, 1.90.
Found: C, 48.48; H, 5.92; N, 1.88.
Bis-[4-O-(2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl)-2,3,6-tri-O-acetyl-
1-(S )-b-D-glucopyranosyl] 1,8-octanebisthiohydroximate (11): Obtained as
described above from 4-O-(2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl)-
2,3,6-tri-O-acetyl-1-thio-b-D-glucopyranose (10) and the dioxime 3. The
pure product 11 was recovered after purification by column chromatography
(EtOAc/petroleum ether (7 : 2 v/v). Product 11 (86% yield): solid, m.p.
118–120ꢀC; Rf 0.48 (EtOAc/petroleum ether 7 : 2 v/v); [ꢁ]D þ 61ꢀ (c, 1.0,

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2926
LAFONT ET AL.
CHCl3); 1H NMR (CDCl3) ꢀ 1.46 (m, 4H, 2CH2), 1.69 (m, 4H, 2CH2), 2.01,
2.03, 2.04, 2.04, 2.06, 2.11, 2.15 (7s, 42H, 14CH3COO), 2.55 (m, 4H,
2CH2C¼NOH), 3.80 (ddd, 2H, J4,5 ¼ 9.8 Hz, J5,6a ¼ 2.4 Hz, J5,6b ¼ 5.1 Hz,
2H-5), 3.99 (ddd, 2H, J4 ,5 ¼ 9.6 Hz, J5 ,6 a ¼ 4.1 Hz, J5 ,6 b ¼ 2.1 Hz, 2H-50),
0
0
0
0
0
0
0
0
4.03 (dd, 2H, J3,4 ¼ 8.9, J4,5 ¼ 9.8 Hz, 2H-4), 4.07 (dd, 2H, J6 a,6 b ¼ 12.5 Hz,
2H-60b), 4.24 (dd, 2H, J6a,6b = 12.1 Hz, 2H-6b), 4.26 (dd, 2H, 2H-60a), 4.46
0
0
0
0
0
(dd, 2H, 2H-6a), 4.87 (dd, 2H, J1 ,2 ¼ 4.0 Hz, J2 ,3 ¼ 10.5 Hz, 2H-2 ), 4.92 (dd,
0
0
0
2H, J1,2 ¼ 9.8 Hz, J2,3 ¼ 8.9 Hz, 2H-2), 5.06 (dd, 2H, J3 ,4 ¼ 9.5 Hz, 2H-4 ),
5.11 (d, 2H, 2H-1), 5.36 (dd, 2H, 2H-30), 5.37 (dd, 2H, 2H-3), 5.42 (d, 2H, 2H-
10), 8.68 (s, 2H, 2C¼NOH); 13C NMR (CDCl3) ꢀ 21.00, 21.00; 21.00, 21.09,
21.10, 21.22, 21.31 (14C, 14CH3COO), 27.09, 28.56, 32.53 (6CH2), 61.94 (2C,
2C-60), 63.47 (2C, 2C-6), 68.34 (2C, 2C-40), 69.01 (2C, 2C-50), 69.64 (2C, 2C-
30), 70.45 (2C, 2C-20), 71.32 (2C, 2C-2), 73.08 (2C, 2C-4), 76.45 (2C, 2C-5),
76.66 (2C, 2C-3), 79.88 (2C, 2C-1), 96.07 (2C, 2C-10), 152.26 (2C, 2C¼NOH),
169.89, 169.89, 170.39, 170.82, 170.99, 170.99, 170.99 (14C, 14CH3COO).
Anal. Calcd. for C60H84N2O36S2 (1473.42): C, 48.90; H, 5.75; N, 1.90.
Found: C, 48.81; H, 6.00; N, 2.05.
Bis-[4-O-(2,3,4,6-tetra-O-acetyl-b-
1-(S )-b- -glucopyranosyl] 1,8-octanebisthiohydroximate (13): Obtained as
described above from 4-O-(2,3,4,6-tetra-O-acetyl-b- -glucopyranosyl)-2,3,6-
tri-O-acetyl-1-thio-b- -glucopyranose (12) and the dioxime 3. The pure prod-
D-glucopyranosyl)-2,3,6-tri-O-acetyl-
D
D
D
uct 13 was recovered after purification by column chromatography
(EtOAc/petroleum ether (7 : 2 v/v). Product 13 (57% yield): solid, m.p.
225ꢀC; Rf 0.48 (EtOAc/petroleum ether 7:2 v/v); [ꢁ]D À 18ꢀ (c, 1.0, CHCl3);
1H NMR (CDCl3) ꢀ 1.40 (m, 4H, 2CH2), 1.64 (m, 4H, 2CH2), 1.98, 2.00,
2.03, 2.03, 2.04, 2.09, 2.11 (7s, 14H, 14CH3COO), 2.50 (m, 4H,
2CH2C¼NOH), 3.67–3.72 (m, 4H, 2H-5,50), 3.80 (dd, 2H, J3,4 ¼ 8.9,
J4,5 ¼ 10.1 Hz, 2H-4), 4.05 (m, 2H, 2H-6b), 4.07 (m, 2H, 2H-60b), 4.38 (dd,
2H, J5 ,6 a ¼ 4.0 Hz, J6 a,,6 b ¼ 12.5 Hz, 2H-60a), 4.49 (dd, 2H, J5,6a ¼ 1.0 Hz,
0
0
0
0
0
0
0
J6a,6b ¼ 12.5 Hz, 2H-6a), 4.52 (d, 2H, J1 ,2 ¼ 7.9 Hz, 2H-1 ), 4.92 (dd, 2H,
0
0
0
0
0
J2 ,3 ¼ 9.1 Hz, 2H-2 ), 5.00–5.05 (m, 4H, 2H-1,2), 5.07 (d, 2H, J3 ,4 ¼ 9.4 Hz,
2H-40), 5.15 (dd, 2H, 2H-30), 5.24 (d, 2H, 2H-3), 8.86 (s, 2H, 2C¼NOH);
13C NMR (CDCl3) ꢀ 20.94, 20.94; 20.94, 21.04, 21.06, 21.06, 21.23 (14C,
14CH3COO), 27.09, 28.64, 32.43 (6C, 6CH2), 61.86 (2C, 2C-60), 62.63 (2C,
2C-6), 68.06 (2C, 2C-40), 70.69 (2C, 2C-2), 71.97 (2C, 2C-20), 72.39 (2C, 2C-
50), 73.26 (2C, 2C-30), 73.94 (2C, 2C-3), 76.60 (2C, 2C-4), 76.70 (2C, 2C-5),
80.08 (2C, 2C-1), 101.23 (2C, 2C-10), 152.21 (2C, 2C¼NOH), 169.65, 169.75,
169.83, 170.35, 170.66, 170.85, 170.95 (14C, 14CH3COO).
Anal. Calcd. for C60H84N2O36S2 (1473.42): C, 48.90; H, 5.75; N, 1.90.
Found: C, 48.74; H, 5.90; N, 1.99.
Bis-[1-(S )-b-D-glucopyranosyl] 1,8-octanebisthiohydroximate (14): Com-
pound 6 (1.75 g, 1.95 mmol) was added to MeOH (100 mL) containing a catalytic

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BIS-DESULFOGLUCOSINOLATES
2927
amount of MeONa and the suspension was stirred till all the compound was
dissolved (16 h). After addition of silica-gel (2 g), the solvent was evaporated and
the solid residue was applied at the top of a column-packed with silica-gel; the
product was eluted with EtOAc/EtOH/H2O (8 : 3 : 1 v/v/v). Compound 14 was
recovered as
a
solid (0.962 g, 88% yield): m.p. 182–183ꢀC; Rf 0.50
(EtOAc/EtOH/H2O 8/3/1 v/v); [ꢁ]D À36ꢀ (c, 0.5, MeOH); 1H NMR (D2O) ꢀ
1.44 (m, 4H, 2CH2), 1.70 (m, 4H, 2CH2), 2.64 (m, 4H, 2CH2C¼ NOH), 3.48
(dd, 2H, J1,2 ¼ 9.8 Hz, J2,3 ¼ 9.0 Hz, 2H-2), 3.51 (dd, 2H, J3,4 ¼ 9.5 Hz,
J4,5 ¼ 9.6 Hz, 2H-4), 3.58 (ddd, 2H, J5,6a ¼ 2.1 Hz, J5,6b ¼ 5.3 Hz, 2H-5), 3.60
(dd, 2H, 2H-3), 3.76 (dd, 2H, J6a,6b ¼ 12.7 Hz, 2H-6b), 3.93 (dd, 2H, 2H-6a),
5.01 (d, 2H, 2H-1).
Anal. Calcd. for C20H36N2O12S2 (560.63): C, 42.84; H, 6.47; N, 4.99.
Found: C, 42.59; H, 6.69; N, 5.05.
Bis-[1-(S )-b-D-glucopyranosyl] 1,12-dodecanebisthiohydroximate (15):
Compound 7 (0.185 g, 0.20 mmol) was added to MeOH (4 mL) containing
a catalytic amount of MeONa and the suspension was stirred for 16 h. After
neutralization with an IR 120 (Hþ) resin, the solution was concentrated to
1 mL and the product was crystallized by addition of EtOAc. Compound 15:
0.107 g, 81% yield: amorphous hygroscopic solid: m.p. 82–83ꢀC; Rf 0.62
(EtOAc/EtOH/H2O 8/3/1 v/v); [ꢁ]D À28ꢀ (c, 0.6, MeOH); the 1H NMR
spectrum was identical to that observed for compound 14 except ꢀ 1.44
(m, 12H, 6CH2).
Anal. Calcd. for C24H44N2O12S2ꢁ2.5H2O (661.774): C, 43.55; H, 7.46;
N, 4.23. Found: C, 43.49; H, 7.55; N, 4.00.
Bis-[4-O-b-D-galactopyranosyl-1-(S )-b-D-glucopyranosyl] 1,8-octane-
bisthiohydroximate (16): Compound 9 (1.75 g, 1.19 mmol) was added to
methanol (150 mL) containing a catalytic amount of MeONa. Dissolution
occurred after a few minutes and the solution was stirred overnight,
becoming like a gel. After a concentration, the residue was dissolved
in water and the solution was neutralized with Amberlyst IR 120 (Hþ).
The pure product 16 (1.02 g, 95% yield) was obtained by concentration:
solid, m.p. 225ꢀC; [ꢁ]D À13ꢀ (c, 0.9, H2O); 1H NMR (C5D5N) ꢀ 1.32
(m, 4H, 2CH2), 1.75 (m, 4H, 2CH2), 2.84 (m, 4H, 2CH2C¼NOH),
3.97–4.58 (m, 24H, 2H-2,20,3,30,4,40,5,50,6a,60a,6b,60b), 5.13 (d, 2H,
0
0
0
J1 ,2 ¼ 7.7 Hz, 2H-1 ), 5.46 (d, 2H, J1,2 ¼ 9.7 Hz, 2H-1), 13.29 (s, 2H,
2C¼NOH); 13C NMR (C5D5N) ꢀ 27.91, 29.32, 32.66 (6C, 6CH2), 61.84,
62.04 (4C, 2C-6,60), 70.06 (2C, 2C-40), 72.46 (2C, 2C-20), 74.18 (2C,
2C-2), 75.12 (2C, 2C-30), 77.22 (2C, 2C-50), 78.24 (2C, 2C-4), 80.71
(2C, 2C-3), 81.40 (2C, 2C-5), 83.30 (2C, 2C-1), 105.70 (2C, 2C-10),
152.48 (2C, 2C¼N–OH).
Anal. Calcd. for C32H56N2O22S2ꢁH2O (902.93): C, 42.56; H, 6.47;
N, 3.10. Found: C, 42.70; H, 6.32; N, 3.10.

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2928
LAFONT ET AL.
Bis-[4-O-a-D-glucopyranosyl-1-(S )-b-D-glucopyranosyl] 1,8-octanebisthio-
hydroximate (17): Compound 11 (1.45g, 0.984 mmol) was added to a
MeOH/NEt3/H2O (2 : 1 : 1 v/v/v) solution (50 mL). The mixture was stirred
overnight; after evaporation of the volatiles, the residue was concentrated
twice from water (2 Â 30 mL) and twice from ethanol (2 Â 25 mL), affording
compound 17 as a solid (0.906 g, 100% yield). A sample of the product was
recrystallized from EtOH. M.p. 148–150ꢀC; [ꢁ]D þ60ꢀ (c, 0.6, H2O); H NMR
1
(D2O) ꢀ 1.42 (m, 4H, 2CH2), 1.68 (m, 4H, 2CH2), 2.62 (m, 4H, 2CH2C¼NOH),
3.39–4.95 (m, 24H, 2H-2,20,3,30,4,40,5,50,6a,60a,6b,60b), 5.00 (d, 2H,
0
J1,2 ¼ 9.8 Hz, 2H-1), 5.44 (d, 2H, J1 ,2 ¼ 3.4 Hz, 2H-1 ); 13C NMR (H2O) ꢀ
27.48, 28.26, 32.17 (6C, 6CH2), 61.00, 61.15 (4C, 2C-6,60), 69.82 (2C, 2C-40),
72.33, 72.63, 73.21, 73.37 (8C, 2C-2,20,30,50), 76.83, 78.07, 79.09 (6C, 2C-3,4,5),
81.93 (2C, 2C-1), 100.21 (2C, 2C-10), 156.50 (2C, 2C¼N–OH).
0
0
Anal. Calcd. for C32H56N2O22S2ꢁ2H2O (920.94): C, 41.73; H, 6.57;
N, 3.04. Found: C, 41.57; H, 6.73; N, 2.89.
Bis-[4-O-b-
D
-glucopyranosyl-1-(S )-b-
D
-glucopyranosyl]
1,8-octanebis-
thiohydroximate (18): Compound 13 (0.390 g, 0.265 mmol) was added to a
MeOH/Et3/H2O (2 : 1 : 1 v/v/v) solution (30 mL). The mixture was stirred over-
night; after evaporation of the volatiles, the residue was concentrated twice from
water (2 Â 10 mL) and twice from ethanol (2 Â 10 mL), affording compound 18 as
a solid (0.239 g), in quantitative yield. Product 18: m.p. 108ꢀC; [ꢁ]D À18ꢀ (c, 0.55,
1
MeOH); H NMR (DMSO þ D2O) ꢀ 1.31 (m, 4H, 2CH2), 1.56 (m, 4H, 2CH2),
2.51
(m,
4H,
2CH2C¼NOH),
2.97–3.63
(m,
24H,
2H-
2,20,3,30,4,40,5,50,6a,60a,6b,60b), 4.28 (d, 2H, J1 ,2 ¼ 7.5 Hz, 2H-1 ), 4.72 (d, 2H,
J1,2 ¼ 9.8 Hz, 2H-1); 13C NMR (DMSO þ D2O) ꢀ 27.69, 27.19, 32.15 (6C, 6CH2),
60.80 (2C, 2C-6), 61.66 (2C, 2C-60), 70.67 (2C, 2C-40), 73.40, 74.01 (4C, 2C-2,20),
76.97 (4C, 2C-30,50), 77.51 (2C, 2C-4), 79.75 (2C, 2C-5), 80.22 (2C, 2C-3), 82.20
(2C, 2C-1), 103.76 (2C, 2C-10), 152.52 (2C, 2C¼N–OH).
0
0
0
Anal. Calcd. for C32H56N2O22S2ꢁH2O (902.93): C, 42.56; H, 6.47;
N, 3.10. Found: C, 42.32; H, 6.53; N, 3.18.
ACKNOWLEDGMENT
Dr. Bruno Perly (SCM, CEA Saclay, France) is gratefully acknowl-
edged for competent NMR assistance.
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BIS-DESULFOGLUCOSINOLATES
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Received in the Netherlands September 27, 2001