Synthesis of ν-triazole derivatives from anomeric sugar diazides

Article abstract of DOI:10.1016/S0008-6215(99)00047-6

Staudinger reaction of acetylated glycopyranosylidene 1,1-diazides led to resonance-stabilized iminophosphoranes (phosphinimines) of 6,7-dihydro[3,4-d]-1,2,3-triazole. This unprecedented transformation involves β-elimination of acetic acid and cycloadditi

Full text of DOI:10.1016/S0008-6215(99)00047-6

Carbohydrate Research 316 (1999) 112–120
Synthesis of n-triazole derivatives from anomeric sugar
diazides
Jo´zsef Kova´cs a, Istva´n Pinte´r a, Ma´ria Kajta´r-Peredy b, Gyula Argay b,
Alajos Ka´lma´n b, Ge´rard Descotes c, Jean-Pierre Praly c,*
a ProChem Research and De6elopment Ltd., H-1525 Budapest, PO Box 17, Hungary
b Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budapest, PO Box 17, Hungary
c Laboratoire de Chimie Organique II, Unite´ Mixte de Recherches CNRS-UCBL no. 5622,
Uni6ersite´ Claude-Bernard Lyon 1, CPE-Lyon, Baˆt 308, 43 boule6ard du 11 No6embre 1918,
F-69622 Villeurbanne, France
Received 17 November 1998; accepted 10 February 1999
Abstract
Staudinger reaction of acetylated glycopyranosylidene 1,1-diazides led to resonance-stabilized iminophosphoranes
(phosphinimines) of 6,7-dihydro[3,4-d]-1,2,3-triazole. This unprecedented transformation involves b-elimination of
acetic acid and cycloaddition of azide anion to the resulting C-2 double bond. Transformation of the new fused
heterocyclic iminophosphoranes on treatment with aqueous ethanolic ammonia gives carboxamidine derivatives of
n-triazole bearing a chiral trihydroxypropyl side-chain. Crystal structure of 5-(D-erythro-1%,2%,3%-trihydroxypropyl)-
1,2,3-triazole-4-carboxamidine was established by X-ray crystallography. © 1999 Elsevier Science Ltd. All rights
reserved.
Keywords: Azido sugars; Glycopyranosylidene 1,1-diazides; Iminophosphoranes (phosphinimines); Pyrano[3,4-d]-1,2,3-triazole;
Staudinger reaction; X-ray structure
recently focused on the Staudinger reaction of
bifunctional glycosyl azides (e.g. 1–4) bearing
an additional substituent at the anomeric car-
bon atom. As preliminaries of these studies,
we have reported [9] the reaction of 2,3,4,6-te-
Introduction
Iminophosphoranes (phosphinimines) of
sugars [1], easily available by Staudinger reac-
tion [2] of the corresponding azido com-
pounds, are advantageous precursors of
various N-containing carbohydrate derivatives
(epimines, carbodiimides, cyclic carbamates,
ureido- and guanidino sugars, etc.) [3–8]. Our
interest in new synthetic pathways involving
transformations via sugar phosphinimines has
tra-O-acetyl-D-glucopyranosylidene
1,1-di-
azide (1) [10–12] with triphenylphosphine to
give a novel n-triazole-fused sugar phosphin-
imine (5). Recently, the anomalous Staudinger
reactions of (1R)2,3,4,6-tetra-O-acetyl-1-
azido- -galactopyranosyl cyanide [13,14] and
D
its carboxamide analogue [14] have been de-
scribed [15]. Investigating the scope and limi-
tations of these transformations, we now
report on the further application of the
* Corresponding author. Tel.: +33-472-43-1161; fax: +
33-478-89-8914.
E-mail address: jean-pierre.praly@univ-lyon1.fr (J.-P.
Praly)
Staudinger reaction to anomeric diazides (
D-
gluco, -galacto, -manno series).
D
D
0008-6215/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(99)00047-6

J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
113
Table 1
1H NMR dataa (400 MHz) for compounds 5–7 and 9
Chemical shifts (l)
P-phenyl
Coupling constants (Hz)
J5,6a J5,6b J6a,6b
Compound Solvent
H-4 H-5 H-6a H-6b Ac
Hortho Hpara Hmeta NH2 OH J4,5
5
6
7
7
9
CDCl3
CDCl3
6.29 4.67 3.88
ddd dd
3.69
dd
2.06 7.84 7.73 7.61
1.85
3.7
2.6
4.9
4.6
4.4
3.9
4.2
5.4
12.1
d
6.38 4.71 4.19
ddd dd
3.81
dd
1.97 7.83 7.73 7.61
1.89
7.4 11.9
6.5 11.0
7.0 11.9
6.6 11.7
d
(CD3)2SO 4.90 3.75 3.41
ddd dd
3.29
dd
8.82 6.34 5.0
d
8.03 4.96
4.48
D2O
D2O
5.18 4.08 3.75
ddd dd
3.52
dd
5.7
d
5.15 3.94 3.57
ddd dd
3.50
dd
6.0
d
a Listed according to parent sugar numbering.
mechanism suggested earlier [9] involving b-
elimination of acetic acid and cycloaddition of
azide anion to the resulting C-2 double bond.
Results and discussion
We have found that the outcome of the
reaction of 1 with triphenylphosphine is inde-
pendent of the molar ratio of the reactants.
Using triphenylphosphine in a slight excess
(1.1 mol) 5 was obtained in a yield of 86%,
while a large excess (3 mol) of triphenylphos-
phine afforded 82% yield of 5, and the unre-
acted reagent could be recovered from the
reaction mixture.
On treatment with triphenylphosphine, the
D
-
galacto diazide 3 gave the epimeric fused tria-
zole derivative 6, which exhibited very similar
NMR signals to those of 5 (Tables 1 and 2).
The 31P NMR spectra of 5 and 6 exhibited
signals at l 23.87 and 24.13, respectively,
which are downfield shifted with respect to the
31P chemical shift value in sugar phosphin-
imines, but are at much a higher field than
that of aminophosphonium salts [4,5]. This is
in good agreement with the resonance-stabi-
lized structure of 5 and 6 revealed by the
X-ray analysis of 5 [16]. As a consequence of
their delocalized electronic structure, 5 and 6
show quite low reactivity. Thus, they do not
react with cumulated double-bond systems,
e.g., with carbon dioxide, in contrast to simple
sugar phosphinimines.
The novelty of the transformation 1“5
prompted the extension of this reaction to the
analogous
glycopyranosylidene 1,1-diazides (2 and 3, re-
spectively) [12]. Reaction of with
D
-manno and
D
-galacto configured
2
triphenylphosphine in dry ether at room tem-
perature (rt) gave the same compound (5), as
obtained from 1, in accord with the reaction

114
J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
0
3
6
2
2
3
Attempted deacetylation of the triazole-
1
1
fused sugar phosphinimines (5 and 6) by the
Zemple´n method gave very complex mixtures
that could not be analysed. However, reaction
of 5 with ethanolic aqueous ammonia could
be well monitored by TLC showing the for-
mation of two products besides triphenylphos-
phine oxide. The product isolated in 48% yield
8
1
1
1
4
2
1
102
after 2 days reaction proved to be 5-( -ery-
D
thro-1%,2%,3%-trihydroxypropyl)-1,2,3-triazole-4-
carboxamidine (7). Work-up of the reaction
mixture at this stage by dry column flash
chromatography [17] led to the isolation of the
minor product 8 in the form of its acetic acid
salt. NMR data for 7 and 8 revealed very
similar molecular structures of both com-
pounds having the same trihydroxypropyl side
chain. In the case of 7 the structure was
corroborated by X-ray analysis which proved
3
the conservation of the
D
-erythro configura-
tion, as well as the symmetrical, delocalized
structure of the carboxamidinium moiety. In
addition to the geometrical parameters, (e.g.
the N–N and N–C multiple bond lengths fall
,
in the range 1.324(2)–1.351(2) A, as seen from
Table 6), the electronic structure of the n-tria-
zole-ring depicted as 7 is substantiated by the
hydrogen bond network (Fig. 1) in which all
endocyclic nitrogen atoms N-3, N-4 and N-5
act exclusively as acceptors. The complex hy-
drogen bond network in which all proton
donor moieties participate in six intermolecu-
lar contacts formed between the homochiral
molecules accounts for the high packing co-
efficient of 0.78 and crystal density of 1.60
g/cm3 found for 7.
2
2
5
2
0
0
1
1
1
8
5
8
The transformation of 5 can be explained
by the nucleophilic attack of ammonia at the
anomeric carbon followed by the opening of
the pyranoid ring and deacetylation to give
the intermediate triphenylphosphoranylidene-
carboxamidine (8). Hydrolysis of 8—as
shown by NMR as well as by preparative
experiment—results in the formation of
amidine 7 with the elimination of tri-

J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
115
phenylphosphine oxide. Under analogous
conditions, the -galacto n-triazolo-pyranosyl
phosphinimine (6) furnished the amidine 9
differing from 7 only in the absolute
configuration of C-4 (according to the par-
ent sugar numbering).
The transformation of glycopyranosylidene
1,1-diazides with triphenylphosphine to give
a dihydropyrano[3,4-d]-n-triazole ring system
requires the presence of a good leaving
group attached at C-3 in order to facilitate
the formation of a C-2–C-3 double bond by
1,2-elimination [9]. Therefore, replacing ace-
toxy groups by benzyloxy moieties having
lower nucleofugacity may very much influ-
ence the outcome of the reaction. Indeed,
the benzylated diazide (4) [10,12] disappeared
only with an excess of triphenylphosphine
(1.5 mol) within 4 days, resulting in a multi-
component mixture that could be partially
separated by column chromatography to
pyrano[3,4-d]-1,2,3-triazole ring-system, not
formed from the corresponding benzylated
derivatives. On treatment with ethanolic am-
monia, these unprecedented sugar-derived
iminophosphoranes gave in good yields new
n-triazole derivatives substituted by a chiral
trihydroxypropyl chain.
D
Table 3
Crystal data and structure refinementa
Empirical formula
Formula weight
Temperature (K)
C6H11N5O3
201.20
293(2)
,
Radiation and wavelength (A)
Crystal system
Space group
Cu Ka; u=1.54180
orthorhombic
P212121
Unit cell dimensions
,
a (A)
6.210(1)
7.097(1)
18.904(1)
833.14(18)
4
,
b (A)
,
c (A)
V (A )
3
give, unexpectedly, 2,3,4,6-tetra-O-benzyl-
mannono-1,5-lactone (10) and 2,3,4,6-tetra-
O-benzyl- -mannonamide (11) in moderate
D
-
,
Z
Dcalc (Mg/m3)
1.604
D
Absorption coefficient, v
1.116
yields (22 and 17%, respectively) in addition
to triphenylphosphine oxide. Structures of 10
and 11 were proved by NMR data in accor-
dance with the literature [18,19].
(mm−1
)
F(000)
424
Crystal description
Crystal size (mm)
colourless, plate
0.25×0.25×0.05
Theta range for data collection 4.685q575.91
The mechanism of the reaction may be in-
terpreted by the pathway presented in
Scheme 1. The gluco configured cation 12,
formed from 4 by the Staudinger reaction of
one of the azido groups and subsequent
elimination of an azide anion, cannot be sta-
bilised by b-elimination as in the case of the
acetyl analogue [9] because the benzyloxy
group is a worse leaving group. Instead, de-
protonation and protonation—involving the
1,2-unsaturated intermediate 13—may either
regenerate 12 or give the manno configured
cation 14. Hydrolysis of 14 (which seems to
be the thermodynamically favoured interme-
diate) during the chromatographic separation
may furnish both the cyclic lactone (10) and
the acyclic mannonamide (11).
(°)
Index ranges
−75h57; −85k58;
−235l523
2180
Reflections collected
Completeness to 2q (%)
Independent reflections
Absorption correction
99.9
1728 [Rint=0.0183]
semi-empirical from
psi-scans
0.9463 and 0.7678
full-matrix least squares
on F2
Max./min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Extinction coefficient
1728/0/139
1.056
0.0050 (11)
R1=0.0394,
wR2=0.1045
R1=0.0400,
wR2=0.1049
0.1(3)
Final R indices [I\2|(I)]
R indices (all data)
Absolute structure parameter
Max. and mean shift/esd
Largest difference peak and hole 0.432 and −0.267
(e A
0.000, 0.000
In conclusion, the anomalous Staudinger
reaction of acetylated glycopyranosylidene
diazides with triphenylphosphine results in
−3
,
)
a Weighting scheme used: w=1/[|2(F2o)+(0.0680*P)2+
0.28*P] where P=[Max (Fo2, 0)+2*F2c]/3. Extinction correc-
the
formation
of
fused
heterocyclic
iminophosphoranes containing 6,7-dihydro-
tion formula: F*=kFc[1+0.001×F2cu3/sin(2q)]−1/4
.
c

116
J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
Fig. 1. Perspective view of 7, showing the hydrogen contacts.
Scheme 1.
Experimental
angles of 25 (36.345q541.60°) reflections.
Intensity data were collected on an Enraf–
Nonius CAD4 diffractometer (graphite
monochromator; Cu–Ka radiation, u=
1.54180 A) at 293(2) K in the range 4.685
q575.91° (index range −75h57;
−85k58; −235l523) using ꢀ–2q scans.
The intensities of three standard reflections
were monitored regularly every 60 min. The
intensities of the standard reflections remained
constant within the experimental error
throughout the data collection. The structure
was solved by direct methods [20] and refined
by anisotropic full matrix least-squares on F2
[21]. Crystal data and refinement details are
shown in Table 3. Hydrogen atomic positions
were calculated from assumed geometries,
General methods.—TLC was performed on
aluminium sheets coated with Silica Gel 60
F254 (E. Merck); detection by UV light and
charring with H2SO4. Column chromatogra-
phy and dry column flash chromatography
[17] were carried out on Silica Gel 60 (E.
Merck, 230–400 mesh). Melting points were
measured in a Bu¨chi apparatus and are uncor-
rected. Optical rotations were determined with
a Zeiss Polamat A polarimeter at 25 °C. IR
spectra were taken with a Nicolet FT 205
spectrometer and the Raman spectra on a
Nicolet 950 FT Raman spectrometer. NMR
spectra were recorded on a Varian VXR-400
spectrometer. Spectral assignments were based
on standard 1D and 2D NMR methods.
,
31
Chemical shifts of the P NMR spectra refer
to 85% aqueous phosphoric acid. FAB mass
spectra were obtained with VG ZAB-SEQ
mass spectrometer using a 3-nitrobenzylalco-
hol matrix.
1 Tables of atomic coordinates, bond lengths, and bond
angles have been deposited with the Cambridge Crystallo-
graphic Data Centre under the deposit No CCDC 113397.
These tables may be obtained, on request, from the Director,
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge, UK, CB2 1EZ.
X-ray data1.—Unit cell parameters of 7
were determined by least squares of setting

J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
117
Table 4
which allowed the C–H, N–H and O–H dis-
tances to be refined. Neutral atomic scattering
factors and anomalous scattering factors were
taken from [22]. Final atomic parameters for
non-hydrogen atoms are listed in Table 4. The
geometry parameters of hydrogen bonds are
given in Table 5, while bond lengths and
relevant torsion angles are given in Tables 6
and 7.
Atomic coordinates (×104) and equivalent isotropic displace-
2
3
,
ment parameters (A ×10 )
a
x
y
z
Ueq
C-1
C-2
C-3
C-4
C-5
C-6
O-4
O-5
O-6
N-1
N-2
N-3
N-4
N-5
347(3)
361(3)
526(3)
879(3)
3200(3)
3573(3)
−514(2)
4730(2)
5747(2)
255(3)
5582(2)
3530(2)
2282(2)
2521(2)
3138(3)
2975(3)
3905(2)
1931(2)
3368(2)
6563(2)
6446(2)
2490(2)
692(2)
5377(1)
5406(1)
5973(1)
6754(1)
6933(1)
7726(1)
7062(1)
6602(1)
7912(1)
5960(1)
4760(1)
4809(1)
4995(1)
5700(1)
23(1)
21(1)
21(1)
22(1)
24(1)
29(1)
29(1)
32(1)
40(1)
33(1)
32(1)
23(1)
25(1)
25(1)
(6R,7S) - 6 - Acetoxymethyl - 7 - acetoxy - 4-
(triphenylphosphoranylideneamino) - 6,7 - di -
hydropyrano[3,4-d]-1,2,3-triazole (5).—(a) To
a stirred solution of 1 [10,12] (192 mg, 0.463
mmol) in dry Et2O (3 mL), was added a
solution of PPh3 (134 mg, 0.511 mmol) in the
same solvent (2 mL). Precipitation of the
product started within 5 min. The reaction
mixture was stored in a cool dark place for 1
night then filtered and washed with dry Et2O
(2 mL) to give 5 as pale yellow crystals; 210
mg (86%), mp 193–194 °C. Recrystallisation
from a CHCl3 solution on saturation with
Et2O gave nice colourless needles, mp 199–
200 °C; [h]D +8° (c 2.3, CHCl3), +17° (c 2,
AcOH); IR (KBr): 1750, 1613, 1574, 729, and
695 cm−1; Raman (solid): 1608, 1592, 1584,
1575, 1026, and 1002 cm−1. FABMS: m/z 529
[M+H]+. Anal. Calcd for C28H25N4O5P
(528.52): C, 63.63; H, 4.77; N, 10.60; P, 5.86.
Found: C, 63.31; H, 4.89; N, 10.31; P, 5.58.
(b) Reaction of 1 (122 mg, 0.295 mmol) and
PPh3 (235 mg, 0.897 mmol) in dry Et2O (9
mL) was performed as described in (a). After
filtration of 5 (128 mg, 82%; mp 192–193 °C)
the mother liquor was concentrated and the
residue extracted with petroleum ether. Evap
oration of the solvent gave unreacted PPh3
(147 mg, 63%), identical with an authentic
sample.
436(3)
241(2)
304(3)
469(3)
543(2)
a Ueq is defined as one third of the trace of the orthogonal-
ized Uij tensor.
(c) Reaction of 2 [12] (94 mg, 0.227 mmol)
and PPh3 (66 mg, 0.25 mmol) in dry Et2O as
described above gave 5 (80 mg, 67%), mp
198–200 °C (from CHCl3/Et2O), identical
with the product in (a).
(6R,7R) - 6 - Acetoxymethyl - 7 - acetoxy - 4-
(triphenylphosphoranylideneamino) - 6,7 - di -
hydropyrano[3,4-d]-1,2,3-triazole (6).—Reac-
tion of 3 [12] (216 mg, 0.52 mmol) and PPh3
(157 mg, 0.6 mmol) was carried out as de-
scribed for the preparation of 5 to give 6 as a
pale yellow solid; 197 mg (71%), mp 190–
192 °C (from CH2Cl2/Et2O); [h]D −38° (c 0.9,
AcOH); IR (KBr): 1750, 1744, 1605, 1572,
730, and 692 cm−1; FABMS: m/z 529 [M+
H]+. Anal. Calcd for C28H25N4O5P (528.52):
C, 63.63; H, 4.77; N, 10.60. Found: C, 63.40;
H, 4.80; N, 10.39.
Table 5
Geometry parameters for hydrogen bonds
,
,
,
D–H···A[symm.]
D–H (A)
H···A (A)
D···A (A)
BD–H···A (°)
N-1–H-1b···O-4[x, y, z]
N-1–H-1a···N-5[x, y+1, z]
N-2–H-2a···N-4[x, y+1, z]
O-4–H-4a···O-6[x−1, y, z]
O-5–H-5a···N-3[x+1/2, −y+1/2, −z+1]
O-5–H-5a···N-4[x+1/2, −y+1/2, −z+1]
O-6–H-6···O-5[x+1, y+1/2, −z+3/2]
N-2–H-2b···N-3[x, y, z]
0.88
0.88
0.89
0.82
0.92
0.92
0.91
0.89
2.02
2.00
2.18
2.12
1.80
2.61
1.81
2.48
2.849(2)
2.871(2)
3.047(2)
2.850(2)
2.716(2)
3.475(2)
2.707(2)
2.812(2)
157.0
168.3
164.8
147.9
172.0
156.8
164.8
102.2

118
J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
Table 6
,
Bond distances (A)
,
,
Atom 1
Atom 2
Dist. (A)
Atom 1
Atom 2
Dist. (A)
C-1
C-1
C-2
C-3
C-4
C-5
N-3
N-1
C-2
C-3
C-4
C-5
C-6
N-4
1.305(2)
1.457(2)
1.394(2)
1.503(2)
1.544(2)
1.520(2)
1.324(2)
C-1
C-2
C-3
C-4
C-5
C-6
N-4
N-2
N-3
N-5
O-4
O-5
O-6
N-5
1.319(2)
1.351(2)
1.338(2)
1.432(2)
1.424(2)
1.423(2)
1.341(2)
Reaction of 5 with aqueous ethanolic ammo-
nia.—(a) A solution of 5 in a mixture of
concd aq ammonia (4 mL) and EtOH (8 mL)
was stored at rt for 2 d. Monitoring by TLC
(3:2:1:1 BuOAc–AcOH–EtOH–H2O) showed
no starting material but the formation of two
products (Rf 0.5 and 0.3) besides Ph3PO (Rf
0.9). The mixture was concentrated and dried
by co-evaporation with EtOH. The residue
was then crystallised from EtOH (4 mL) at
J5,6b 6.9 Hz, J6a,6b 12.0 Hz, H-6b). (A repeated
1H NMR measurement after 2 weeks indi-
cated a complete conversion of 8·AcOH into
7). Anal. Calcd for C26H28N5O5P (521.53): C,
52.21; H, 5.41; N, 13.43. Found: C, 52.56; H,
5.53; N, 12.95.
(b) On treatment of 5 (211 mg, 0.4 mmol)
with a mixture of concd aq ammonia (4 mL)
and EtOH (8 mL) for 2 days, 7 (36 mg, mp
210–211 °C) was obtained by crystallisation
from EtOH as described in (a). The ethanolic
filtrate was concentrated and the residue, dis-
solved in water (3 mL), was stirred for 5 days.
TLC (3:2:1:1 BuOAc–AcOH–EtOH–H2O)
showed the transformation of the intermediate
8 (Rf 0.5) into 7 (Rf 0.3). The separated crys-
tals were then filtered to give Ph3PO (90 mg,
81%, mp 148–151 °C), identical with an au-
thentic sample. The aq filtrate was concen-
trated and the residue crystallised from EtOH
to afford an additional crop of 7, 32 mg, mp
206–210 °C, total yield 68 mg (85%).
0 °C to give 5-( -erythro-1%,2%,3%-trihydroxy-
D
propyl)-1,2,3-triazole-4-carboxamidine (7, 39
mg, 48%); beige solid, Rf 0.3 (3:2:1:1 BuOAc–
AcOH–EtOH–H2O); mp 210–211 °C. Re-
crystallisation by adding acetone to a concd
aq solution of 7 gave colourless crystals, mp
214 °C; [h]D +4° (c 2, H2O); IR (KBr): 3600–
2400 (broad), 1694, and 1576 cm−1; Raman
(solid) 1649 and 1576 cm−1, FABMS: m/z 202
[M+H]+. Anal. Calcd for C6H11N5O3
(201.19): C, 35.82; H, 5.51; N, 34.81. Found:
C, 35.61; H, 5.54; N, 34.28.
The EtOH mother liquor was then sub-
jected to dry column flash chromatography
[17] using acetone–AcOH mixtures with in-
creasing proportion of the latter from 95:5 to
5:1. Eluted first was Ph3PO (73 mg, 66%, mp
150–153 °C) identical with an authentic sam-
5-( -threo-1%,2%,3%-Trihydroxypropyl)-1,2,3-
D
triazole-4-carboxamidine (9).—A solution of 6
in a mixture of concd aq ammonia (6 mL) and
EtOH (12 mL) was left to stand for 2 days,
then concentrated. The residue was stirred
with water (8 mL) for a week, then decanted.
The aq soln was concentrated to a small vol-
ume (1–2 mL) and mixed with acetone to give
9 (65 mg, 59%), as pale yellow crystals, mp
207–210 °C, Rf 0.3 (3:2:1:1 BuOAc–AcOH–
EtOH–H2O); [h]D −4° (c 2.4, H2O); IR
(KBr): 3600–2400 (broad), 1685, and 1577
cm−1; FABMS: m/z 202 [M+H]+. Anal.
Calcd for C6H11N5O3 (201.19): C, 35.82; H,
5.51; N, 34.81. Found: C, 35.49; H, 5.56; N,
34.31.
ple. Eluted second was 5-( -erythro-1%,2%,3%-tri-
D
hydroxypropyl) - 1,2,3 - triazole - 4 - (triphenyl-
phosphoranylidene-carboxamidinium acetate
(8·AcOH), as a white solid, Rf 0.5 (3:2:1:1
BuOAc–AcOH–EtOH–H2O); mp 182 °C
(dec); [h]D +11° (c 2, AcOH); IR (KBr):
3600–2400 (broad), 1690, 1570, 730, and 697
1
cm−1. H NMR (D2O, 400 MHz): l 5.36 (d,
1H, J4,5 5.8 Hz, H-4); 3.97 (ddd, 1H, H-5);
3.55 (dd, 1H, J5,6a 3.8 Hz, H-6a); 3.41 (dd, 1H,

J. Ko6a´cs et al. / Carbohydrate Research 316 (1999) 112–120
119
tone); [a]D +14° (c 1.8, CHCl3). Lit [19] mp
132–134 °C, [a]D +15.8° (c 0.55, CHCl3). IR
(KBr): 3440, 1645, 738, and 695 cm−1. The 1H
NMR data were in good agreement with pub-
lished data [19]. Eluted third was Ph3PO (396
mg, 99%), mp 152–154 °C (from cyclohex-
ane), identical to an authentic sample.
Table 7
Relevant torsion angles (°)
Atom 1
Atom 2
Atom 3
Atom 4
Torsion angle
N-3
C-2
N-3
C-2
C-3
N-1
N-2
C-1
N-3
C-1
C-2
C-2
O-4
C-3
C-3
O-5
C-4
C-2
C-3
N-4
N-3
C-2
C-1
C-1
C-2
C-2
C-2
C-3
C-3
C-4
C-4
C-4
C-5
C-5
C-3
N-5
N-5
N-4
N-3
C-2
C-2
C-3
C-3
C-3
C-4
C-4
C-5
C-5
C-5
C-6
C-6
N-5
N-4
C-3
N-5
N-4
C-3
C-3
N-5
C-4
C-4
O-4
C-5
O-5
O-5
C-6
O-6
O-6
−0.9(2)
0.8(2)
−0.4(2)
−0.1(2)
0.6(2)
−8.0(3)
171.7(2)
−179.6(2)
174.4(2)
−4.3(3)
48.7(3)
−71.6(2)
−175.3(1)
−51.3(2)
−168.8(2)
54.8(2)
Acknowledgements
This work was supported by the Hungarian
Scientific Research Fund (OTKA T 14939 and
T 23371), by the Academic Research Fund
(AKP 96/2-427 2,4) and jointly by the Centre
National de la Recherche Scientifique (project
no. 2811) and the Hungarian Academy of
Science.
174.8(2)
References
The water-insoluble part of the reaction
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mg, 68%), mp 153–155 °C, identical to an
authentic sample.
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120
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