Hydrophosphorylation of monosaccharides oximes and hydrazones

Article abstract of DOI:10.1134/S1070363209080064

The hydrophosphorylation of monosaccharides oximes and hydrazones was studied; similarity and difference of this process compared to the reaction of secondary glycosylamines with the hydrophosphoryl compounds are shown. A number of the original α-aminophosphoryl compounds is obtained including those containing carbohydrate fragment in their compositions.

Full text of DOI:10.1134/S1070363209080064

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1622–1631. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.A. Bobrikova, M.P. Koroteev, I.I. Levina, and E. E. Nifant’ev, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 8,
pp. 1264–1273.
Hydrophosphorylation
of Monosaccharides Oximes and Hydrazones
A. A. Bobrikovaa, M. P. Koroteeva, I. I. Levinab, and E. E. Nifant’eva
a Moscow Pedagogical State University,
Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: nastenka-bobrik@yandex.ru
b Emmanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia
Received March 6, 2009
Abstract—The hydrophosphorylation of monosaccharides oximes and hydrazones was studied; similarity and
difference of this process compared to the reaction of secondary glycosylamines with the hydrophosphoryl
compounds are shown. A number of the original α-aminophosphoryl compounds is obtained including those
containing carbohydrate fragment in their compositions.
DOI: 10.1134/S1070363209080064
α-Aminophosphonates and the constructions close
to them by structure are of significant chemical interest
due to variety of the areas of their application. Among
these compounds are found the substances possessing
biocontrol activity of different types [1, 2], the com-
pound capable of the directed transport of substances
through membranes [3], extractants [4, 5] etc. Special
attention deserve the products of aminophosphoryla-
tion of natural or related objects. Many publications
and reviews describe the synthesis and properties of
the phosphoric analogs of aminoacids [6, 7]. At the
same time the aminophosphoryl compounds con-
taining carbohydrate fragments are considerably less
studied [8], although they can be widely used, for
example, for studying many problemsconcerning the
sugars metabolism on the molecular level, and for
understanding the structure of the active centers of the
corresponding enzymes.
azomethine, and the influence was revealed of the
sugar fragment nature and the structure of the radical
connected with the NH group on the process of the
phosphorylation [9–11].
This work concerns to the application of the
method of synthesis of the carbo-hydrates amino-
phosphoryl derivatives proposed by us to the design of
the compounds containing in their structure hydro-
xylamine and hydrazine fragments. It is important to
note that obtaining of aminophosphoryl derivatives
from simplest oximes by addition of hydrophosphoryl
compounds has been described [5, 12–14]. Further-
more, there are data, that the nitrones prepared from
mannose oximes with protected hydroxyl groups have
been successfully used for the synthesis of amino-
phosphonates with the N-glycoside fragment as the
amino components [15]; however, connecting the
phosphorus-containing group with the anomeric
carbon atom of these compounds has not been
attempted earlier. Note that aminophosphonates of
simple structure containing hydrazine fragments are
known, but they were obtained by other methods: by
the amino group substitution for hydroxy or sulfonic
groups in phosphonates with the appropriate structure
or by the addition of hydrazines to the derivatives of
pentavalent phosphorus containing allyl group [16,
17]. We did not find in literature any data on the
carbohydrate-containing aminophosphoryl derivatives
with the hydrazine type substituents.
A method of designing the aminophosphoryl
derivatives with a phosphorus atom connected directly
with the carbohydrate residue is the reaction of the
hydrophosphorylation of N-glycosides. This process
has been under investigation in our laboratory for the
last several years. Thus, we examined in detail the
addition of hydrophosphoryl compounds to secondary
glycosylamines. On the example of the phosphoryla-
tion of this group of glycosides we established that the
reaction proceeds through the stage of the glycol-
sylamine ring cleavage with the formation of
1622

HYDROPHOSPHORYLATION OF MONOSACCHARIDES OXIMES
1623
In recent years the monosaccharide oximes and
hydrazones attracted attention of researchers in
connection with the wide use of these substances in the
solution of diverse problems of contemporary fine
organic synthesis, and also due to the detection of their
unusual biological properties [18–23]. In this
connection the development of the methods of
synthesis of aminophosphoryl compounds on their
basis is an important direction of the modification of
these carbohydrate derivatives. Furthermore, their use
in the addition reaction with hydrophosphoryl com-
pounds seems important for the development of
general regularities governing the process of the
reaction of hydrophosphorylation of N-glycosides,
since it is known that monosaccharide oximes and
hydrazones exist in solutions predominantly in the
open-chain form [24–27]. Many of these compounds
retain linear structure in the solid state [28]. At the
same time, both oximes and hydrazones of sugars in
the solutions are capable of the mutarotation [27, 29].
Thus, predominant existence of these compounds in
the linear form rather than as glycoside will make it
possible to compare their reactivity in the process of
hydrophosphorylation with the activity in this reaction
of glucosamines, where the shift of tautomeric
equilibrium glucosylamine–imine to the side of the
cyclic structure is characteristic [24].
We began this investigation with brinding into the
reaction of hydrophosphorylation of the mono-
saccharides oximes and hydrazones with free hydroxy
groups. As initial sugars we selected D-xylose and D-
glucose, the representatives of pentoses and hexoses
respectively. Phenylhydrazones of these monosac-
charides (Ia, Ib) were obtained by condensation with
the phenylhydrazine employing known procedures
[25]. The data of 13C NMR spectroscopy of these
compounds showed that they exist in solution in the
form of the derivatives, which contain in their structure
linear sugar fragment and C=N bond, as can be judged
from the characteristic chemical shift of the carbon C1
nucleus in the region of 145–147 ppm.
Compounds Ia, Ib were reacted with diphenylphos-
phinous acid and with phenyl phenylphosphonite
known as effective phosphorylating reagents in this
reaction [10] (Scheme 1).
Scheme 1.
N
NHPh
HC
Ph
R'
O
H
HO
H
OH
PhR'P(O)H
DMF, 80oС, 8 h
P
H
*
R
CH
NH
NHPh
O
_3 HOH
OH
OH
H
R
Ia, Ib
IIa_IIc
Ia: R = H, Ib: R = CH2OH; IIa: R = H, R' = Ph, IIb: R = CH2OH, R' = Ph, IIc: R = H, R' = OPh.
We expected moderate activity of hydrazones in
ampules without the use of a catalyst. According to the
data of 31P NMR spectroscopy, reaction of
phenylhydrazones Ia, Ib with hydro-phosphoryl
compounds requires 8 h to be completed. It is
established that the nature of sugar and of the
phosphorylating reagent in this case does not affect the
reaction rate of the hydrophosphorylation (at the
phosphorylation of glycosylamines these differences
have been observed [9, 10]). Apparently, the predo-
minance of the linear form of hydrazones in the
the addition reaction with hydrophosphoryl com-
pounds in comparison with glycosylamines. This is
connected with the presence next to C=N fragment of
the electron-acceptor groups, which have an essential
effect on reactivity of N-glycosides in the reaction of
hydrophosphorylation [11], and also with the
predominance in derivatives Ia, Ib in the solutions of
open-chain form. Therefore, introduction of phos-
phoric group was carried out by heating in the sealed
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1624
BOBRIKOVA et al.
solution reduces the influence of the rate of N-
glycoside–azomethine tautomeric transitions on the
reactivity of nitrogen derivatives of monosaccharides
in this process. At the same time, the need of
“trapping” the N-glycoside imine form by the
phosphorylating reagent disappears, therefore the time
and temperature parameters of the reactions with the
use of different derivatives of trivalent phosphorus are
the same.
Ic, Id was carried out (the oximes obtained employing
the procedures in [30, 31]. According to the data of the
13C NMR spectra the oximes are imines with the linear
residue of monosaccharide in the composition of the
molecule). We found that the phosphorylation of xylose
and glucose oximes in all cases proceeds completely in
3 h. The sufficiently short time of reaction of
compounds Ic, Id with hydrophosphoryl compounds
suggested the possibility to carry out this reaction
without heating. Actually, the addition of
diphenylphospinous acid to glucose oxime was com-
pleted at room temperature in two days (Scheme 2).
Under the analogous conditions the addition of hydro-
phosphoryl compounds to xylose and glucose oximes
Scheme 2.
Ph
R'
O
PhR'P(O)H
P
DMF, 80oC, 3 h
*
R
CH
O
N
OH
_3 HOH
HC
NH
HO
H
HO
H
OH
IId_IIf
H
O
Ph
Ph
NH OH
P
*
OH
OH
CH
Ph2P(O)H,
DMF,
H
H
OH
H
25оС, 48 h
R
Ic, Id
HO
H
OH
OH
H
CH2OH
III
Ic: R = H, Id: R = CH2OH; IId: R = H, R' = Ph, IIe: R = CH2OH, R' = Ph, IIf: R = H, R' = OPh.
Products IIa–IIf, III were purified by shaking with
intramolecular (for example, the formation of the
hydrogen bond between the proton of NH-group and
the oxygen of the furan ring) and intermolecular
interactions in the structure of their molecules together
with the chiral carbon atom appears a “quasi-chiral”
center at the nitrogen atom. Thus, in these cases we
also observed the formation of diastereomers. As a result
it was possible to fix the presence of two enantiomers
relative to carbon atom in the NMR spectra without the
use of the optically active solvents or other additives.
The analysis of the 1H NMR spectra shows that the
products IIa–IIf obtained at heating are the derivatives
of furan. This follows from the absence of the signals
in the region of 3.5–5.5 ppm, characteristic of the
resonance of the protons of carbohydrate fragment. At
active carbon in warm ethanol followed by filtration
through the layer of aluminum oxide. After
purification, these compounds were thick syrups,
sparingly suluble in the majority of organic solvents.
In the 31P NMR spectra of all synthesized com-
pounds two singlet signals appeared equal by integral
intensity, with the chemical shifts in the region of 30–
40 ppm. Furthermore, the broadening of signals in the
1H NMR spectra was addewed. This indicates that the
addition of asymmetric ether of phosphonous acid
leads to the formation of a mixture of two diastereo-
mers in the ratio 1:1. At the same time, the spectral
picture observed at the formation of diphenyl-
phosphine oxides can be due to the fact that at the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

HYDROPHOSPHORYLATION OF MONOSACCHARIDES OXIMES
Table 1. Selected physico-chemical characteristics of compounds IIa–IIf
1625
Comp.
no.
Yield,
%
31P NMR spectrum,
Found/Calculated, %
H
Formula
δP, ppm
C
N
P
51
36.1, 38.9
31.9, 33.2
29.5, 31.6
28.5, 30.7
36.7, 39.2
37.3, 38.9
C23H21N2O2Р
C24H23N2O3Р
C17H16NO3Р
C18H18NO4Р
C23H21N2O3Р
C18H18NO5Р
71.39/71.12
69.31/68.89
65.49/65.17
63.19/62.97
60.85/60.17
68.99/68.31
5.12/5.45
5.17/5.54
5.01/5.15
5.03/5.28
5.01/5.05
5.16/5.23
7.12/7.21
6.10/6.69
4.14/4.47
4.12/4.08
3.81/3.90
6.88/6.93
8.48/7.97
7.68/7.40
9.76/9.89
8.78/9.02
8.90/8.62
7.23/7.66
IIa
49
IIb
IIc
47
46
IId
IIe
32
28
IIf
1
the same time, in the downfield part of the spectrum
together with the signals of the phenyl rings protons of
phosphoryl phenylhydrazine fragments IIa, IIb, IIe in
all cases the resonance of the furan ring protons was
seen. When the reaction between glucose oxime and
diphenylphospinous acid was carried out at room
temperature, compound III was isolated with the linear
carbohydrate residue in the composition of the
molecule, and in the 1H NMR spectrum of this product
all proton signals of glucose appeared the constant 2JHP
for the protons at the C1 carbon atom was 12.6 Hz. The
data of elemental analysis also agree with the proposed
structure of these compounds.
to the data of H NMR spectroscopy, omino fprm is
characteristic for these compounds in solutions with
the linear structure of the monosaccharide residue, as
we judge from the chemical shift of the proton at C1 in
the region of 7–7.5 ppm.
The phosphorylation of compounds IVa, IVb, Va,
and Vb was carried out with the same hydro-
phosphoryl compounds in chloroform at heating in
sealed ampules in the presence of 5 mol % of pyridine
(Schemes 3 and 4). The efficiency of the use of
pyridine as the basic catalyst at the phosphorylation of
protected glycosylamine derivatives we have shown
earlier [9]. The course of the process was monitored by
the method of 31P NMR spectroscopy. Reaction
proceeded for 6 h (in the case of compounds VIa, VIc,
and VId) or for 12 hours (in the case of compounds
VIb, VIe, and VIf).
The yields, data of 31P NMR spectroscopy and
elemental analysis for compounds IIa–IIf are listed in
Table 1.
The obtained results confirm the fact that the
reaction of the monosaccharides oximes and hydra-
zones with hydrophosphoryl compounds proceeds like
in the case of glycosylamines, and after the addition of
the phosphorylating reagent usually occurs dehydra-
tion of the sugar fragment of molecule with the closure
of the furan ring. However, with the monosaccharides
oximes as the substrates a control over the process is
possible by changing the reaction temperature.
Compounds VIa–VIf were purified by column
chromatography. By physical properties they are low-
melting substances or thick syrups, crystallizing during
the storage, soluble in the majority of organic solvents.
Individuality and structures of compounds VIa–VIf
were confirmed by the data of H, C, and P NMR
spectroscopy and elemental analysis.
1
13
31
The following stage of the work was the study of
addition of hydrophosphoryl compounds to the mono-
saccharides oximes and hydrazones protected at the
hydroxyl groups for the purpose of retention of the
carbohydrate part of the molecule in the structure of
the aminophosphoryl compounds. As the substrate for
the phosphorylation we selected 2,3;5,6-di-O-isopro-
pilidenmannose (DIM) oxime (IVa) and phenyl-
hydrazone (IVb), and also xylose and glucose phenyl-
hydrazones complete acetates (Va and Vb). The
diisopropilidenemannose oxime is described in [23],
other substances were obtained for the first time within
the framework of the present investigation. According
In the 31P NMR spectra of the synthesized com-
pounds two singlet signals are found with the chemical
shifts in the region of 30–40 ppm with different ratios
of integral intensity (upfield signal predominates
except for the case of compound VIb). Furthermore,
we observed the doubling or broadening of signals in
1
the H NMR spectra. Obviously the reaction proceeds
with the formation of two diastereomers. The character
of spectra shows that the reaction products are the
aminophosphoryl compounds containing carbohydrate
fragment in their composition. The signals of all
protons have expected values of chemical shifts and
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1626
BOBRIKOVA et al.
Scheme 3.
O
N−R
R'
HC
NH−R
P
Ph
*
CH
O
O
H
H
H
H3C
PhR'POH
H3C
O
H
H
H
3C
C
CHCl3, Py
85oC
O
H
H
H
H
3C
OH
O
OH
O
CH3
CH3
CH3
CH3
C
H2C
O
H2C
O
IVa, IVb
VIa_VIc
IVa: R = OH, IVb: R = NHPh; VIa: R = OH, R' = Ph, VIb: R = NHPh, R' = Ph, VIc: R = OH, R' = OPh.
Scheme 4.
O
R'
N−NH−Ph
HC
P
NH−NH−Ph
Ph
*
CH
H
AcO
H
OAc
H
H
OAc
H
PhR'POH
AcO
H
CHCl3, Py
85oC
OAc
OH
OAc
OH
H
H
R
Va, Vb
R
VId_VIf
Va: R = H, Vb: R = CH2OAc; VId: R = H, R' = Ph, VIe: R = CH2OAc, R' = Ph, VIf: R = CH2OAc, R' = OPh.
2
spin–spin coupling constants. Thus, the constant JHP
ment of the signals was possible only using a method
of double magnetic resonance. The yields, data of P
NMR spectroscopy and elemental analysis for the
value for the protons at the C1 carbon is approximately
13 Hz. Let us note that the H NMR spectra of these
31
1
compounds have a fairly complicated nature, and assign-
compounds VIa–VIf are listed in Table 2.
Table 2. Selected physico-chemical characteristics of compounds VIa–VIf
Comp.
no.
Yield,
%
31P NMR spectrum,
Found/Calculated, %
Formula
δP, ppm
C
H
N
P
55
36.1, 38.9
32.3, 35.5
37.6, 39,4
29.5, 31.6
28.5, 30.7
38.2, 40,6
C24H32NO7Р
C30H37N2O6Р
C24H32NO8Р
C29H33N2O8Р
C32H37N2O10Р
C32H37N2O11Р
11.53/60.37
65.39/65.20
58.85/58.41
61.79/61.26
60.29/60.00
58.90/58.53
6.15/6.75
6.19/6.75
6.41/6.54
5.50/5.85
5.73/5.82
5.42/5.68
2.62/2.93
5.10/5.07
2.69/2.84
4.84/4.93
4.32/4.37
4.24/4.27
7.41/6.49
5.69/5.61
6.94/6.28
5.79/5.45
4.91/4.83
5.18/4.72
VIa
VIb
VIc
VId
VIe
VIf
52
35
49
53
36
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HYDROPHOSPHORYLATION OF MONOSACCHARIDES OXIMES
1627
The results of the present investigation in con-
junction with the data obtained earlier for secondary
glycosylamines [9–11] allow to give a number of
general conclusions. First, the presence of acceptor
substituents in the molecule of monosaccharide oximes
and hydrazones near the imino-group is compensated
by the predominance of the open-chain forms above
the cyclic ones in their solutions, and as a consequence
these carbohydrate derivatives show moderate activity
in the reaction with hydrophosphoryl compounds,
regardless the sugar nature and structure of the phos-
phorylating reagent. These facts confirm the validity of
route of addition reaction of hydrophosphoryl
compounds to N-glycosides the proposed by us, which
includes the stages of ring opening of the molecule of
the sugar nitrogen derivative with the formation of
azomethine followed by the addition of the
phosphorylating reagent at the C=N-bond. Second, the
similarity in the directions of phosphorylation of these
nitrogen derivatives of carbohydrates and of secondary
glycosylamines indicates the general nature of the
addition reaction of hydrophosphoryl compounds to N-
glycosides capable of the ring-chain isomerization in
solutions.
instrument at the operating frequency 161.98 MHz, of
other compounds, on the spectrometer Bruker WP-80
with the operating frequency of 32.4 MHz. The H
1
NMR Spectra were registered on a Bruker H-250
spectrometer with the operating frequency 250 MHz.
The 13C NMR spectra were re-corded on a Bruker AC-
200 spectrometer at the operating frequency 50 MHz.
Spectra were recorded from the solutions in DMSO-d6
(Ia–Id, IIa–IIf, III) or CDCl3 (IV, Va, Vb, VIa–VIf)
with the use of signal of the residual protons of the
deuterated solvent as the internal reference and of 85%
H3PO4 as the external reference. The assignment of the
proton signals was carried out on the basis of the data
of double magnetic resonance. TLC was carried out on
the Silufol UV-254 plates in the system benzene:
acetonitrile:hexane = 4:2:1, the visualoration of spote
achieved by heating. Preparative chromatography was
carried out on a column of 10 mm diameter packed
with silica gel, elution by the system of solvents
benzene:acetonitrile:hexane = 4:2:10. Melting points
were determined in a sealed capillary at a heating rate
1 deg min–1. Optical rotation was determined on a
polarimeter PU-07 from solutions (c = 0.5) in DMSO
(IIa–IIf, III) or CHCl3 (VIa–VIf) at 18°C. For the
elemental analysis was used a Perkin-Elmer 2400
analyzer.
Thus, the studied reaction is a promising method of
preparation of carbohydrates containing phosphine
oxides and phosphinates and makes it possible to
synthesize the original phosphorus-containing deriva-
tives on the basis of N-glycosides with the different
types of glycone and aglycone. Furthermore, in the
course of this investigation a possibility was demon-
strated of obtaining the aminophosphoryl compounds
containing hydrazine fragment using a version of the
Pudovik reactionconvenient in the preparative sense.
N-β-D-Xylopyranosyl-N'-phenylhydrazine (Ia)
was obtained employing the published procedure [25]
from 1.5 g of D-xylose and 1.09 g of phenylhydrazine.
Yield 2.10 g (88%). mp 114–116°C (decomp.). 13C
NMR spectrum, δС, ppm: glycone, 64.8 (C5), 71.6 (C4),
72.0 (C3), 72.3 (C2), 145.8 (C1); aglycone: 111.7 (C2,
C6), 118.2 (C4), 129.1 (C3, C5), 141.1 (C1).
N-β-D-[Glucopyranosyl]-N'-phenylhydrazine (Ib)
was obtained employing literary procedure [25] from
1.8 g of D-glucose and 1.09 g of phenylhydrazine.
Yield 2.30 g (85%). mp 119–121°C (decomp.).
EXPERIMENTAL
In the work were used the monosaccharides, hyd-
roxylamine hydrochloride, phenylhydrazine, Ph2PCl
and PhPCl2 compounds from Aldrich, the silica gel
from Merck with the size of the particles 0.040–
0.063 mm, the aluminum oxide from Acros (activated,
basic, the size of the particles 50–200 μm), activated
carbon from Merck with the granula size 1.5 mm.
Phosphorus chlorides were distilled before use.
13
(published data: 116°C [25]). C NMR spectrum, δC,
ppm: glycone, 63.9 (C6), 69.5 (C5), 70.7 (C4), 70.9
(C3), 71.3 (C2), 145.9 (C1); aglycone: 111.6 (C2, C6),
118.0 (C4), 142.5 (C3, (C5), 146.9 (C1).
N-β-D-xylopyranosyl-hydroxylamine (Ic) was
obtained employing the procedure [30] from 1.5 g of
D-xylose and 1.16 g of hydroxylamine hydrochloride.
Yield 1.00 g (60%). Syrup (published data: syrup
[30]). The 13C NMR spectrum coincides with that in
[30].
All experiments with the use of P(III) reagents
were carried out in an atmosphere of dry argon, with
solvents purified and dried by standard procedures
[32]. The 31P NMR spectra of compounds IIe–IIf, VIc
and VIf were registered on a Bruker Avance-400
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1628
BOBRIKOVA et al.
N-β-D-[Glucopyranosyl]-hydroxylamine (Id) was
0. 1H NMR spectrum, δ, ppm, J, Hz: 5.05 m (2H, NH,
obtained employing procedure [31] from 1.8 g of D-
glucose and 1.16 g of hydroxylamine hydrochloride.
Yield 1.40 g (72%). mp 140–142°C (decomp.).
(published data: 136–137°C [31]). 13C NMR spectrum,
δC, ppm: glycone, 63.6 (C6), 69.4 (C5), 70.2 (C4), 70.5
(C3), 71.7 (C2), 145.8 (C1); aglycone: 111.9 (C2, C6),
118.2 (C4), 142.6 (C3, (C5), 146.1 (C1).
N–CH–P); the furan fragment: 6.20 m [1H, C4H, 3JHH(3)
=
3
4
3.7], 6.29 m [1H, C3H, JHH(4) = 3.7, JHP = 2.5], 7.33
br.s (1H, C5H); the aminophosphoryl fragment: 5.74 br
from (1H, NH), 6.51 br.s (1H, OH), 7.55 m (6H, 2C3H,
2C4H, 2C5H), 7.70 t (2H, C2H, C6H, 3JHP = 10.9), 7.87
t (2H, C2'H, C6'H, 3JHP = 10.7).
{5-[(diphenylphosphoryl)(hydroxylamino)methyl]-
Phosphine oxides IIa–IId (general procedure):
1 mmol of a compound Ia–Id and 1 mmol (0.202 g) of
diphenylphosphosphinous acid were dissolved in 5 ml
of DMF saturated with argon, the solution was placed
into an ampule, the ampule was sealed and heated for
8 h at 80°C (in the bath). After the reaction completion
DMF was removed on a rotary evaporator, 30 ml of
warm ethanol and 0.5 g of active carbon were added to
the residue, and the mixture was shaken to the
clarification. The solution was decanted, 10 ml of
chloroform was added and then the solution was
filtered through 5 cm layer of aluminum oxide in a
column of 1 cm diameter. The sorbent was washed
twice with 10 ml of the system ethanol:chloroform 3:1.
The solvents were removed on a rotary evaporator, the
residue was dried in a vacuum (12 mm Hg) at 70°C for
6 h.
furan-2-yl}methanol (IId). Yield 0.16 g (46%).
Syrup. [α]D = 0. H NMR spectrum, δ, ppm, J, Hz:
1
5.58 m (2H, NH, N–CH–P); the furan fragment: 4.10
m (2H, CH2OH), 4.92 br.s (1H, CH2OH), 6.40 m (2H,
C4H, C3H); the aminophosphoryl fragment: 5.66 br.s
(1H, NH), 6.60 br.s (1H, OH), 7.54 m (6H, 2C3H,
2C4H, 2C5H), 7.73 t (2H, C2H, C6H, 3JHP = 10.8), 7.85
t (2H, C2'H, C6'H, 3JHP = 11.0).
Phosphinates IIe, IIf. 1.2 mmol of compound Ia,
Id and 1.2 mmol (0.262 g) of diphenylphosphonite
dissolved in 6 ml of DMF were placed into an ampule,
the ampule was sealed and heated for 8 h at 80°C (in
the bath), then DMF was removed in a vacuum, 15 ml
of warm ethanol and 0.5 g of activated carbon were
added to the residue, the mixture was shaken to the
clarification of solution, then the solution was
decanted, 5 ml of acetone was added to the solution
and all was filtered through 5 cm layer of silica gel in a
column 1 cm diameter. The silica gel was then twice
washed with the system of solvents ethanol:acetone 3: 1.
The combined filtrate was evaporated to dryness and
the residue was dried at 70°C in a vacuum (12 mm Hg)
for 6 h.
N-(diphenylphosphoryl)(furan-2-yl)methyl]-N'-
phenylhydrazine (IIa). Yield 0.19 g (51%). Syrup.
1
[α]D = 0. H NMR spectrum, δ, ppm, J, Hz: 5.18 m
(2H, NH, N–CH–P); the furan fragment: 6.22 m [1H,
C4H, 3JHH(3) = 3.8], 6.28 m [1H, C3H, 3JHH(4) = 3.8, 4JHP
=
3.4], 7.36 br.s (1H, C5H); the phenylhydrazine frag-
3
ment: 6.88 d (2H, C2H, C6H, JHH = 7.4), 7.02 d (1H,
Ethyl[phenylhydrazino-(2-furyl)methyl]phenyl-
3
3
C4H, JHH = 7.7), 7.21 d.d (2H, C3H, C5H, JHH = 7.4,
phosphinate (IIe). Yield 0.15 g (32%). Syrup. [α]D =
3JHH = 7.7); the phosphoryl fragment: 7.57 m (6H,
1
0. H NMR spectrum, δ, ppm, J, Hz: 5.32 m (1H, N–
2C3H, 2C4H, 2C5H), 7.87 t (2H, C2H, C6H, JHP
=
3
2
CH–P, JHP = 16.4); 5.95 br (1H, NH); the furan
10.6), 7.91 t (2H, C2'H, C6'H, 3JHP = 10.8).
3
fragment: 6.27 m (1H, C4H, JHH = 3.1), 6.42 m (1H,
3
C3H, JHH = 3.1), 7.33 br. s (1H, C5H); the
{5-[(Diphenylphosphoryl)(N'-phenylhydrazino)-
methyl]furan-2-yl}methanol (IIb). Yield 0.21 g (49%).
phenylhydrazine fragment: 6.78 d (2H, C2H, C6H, 3JHH
=
1
3
Syrup. [α]D = 0. H NMR spectrum, δ, ppm, J, Hz:
7.8), 6.97 d (1H, C4H, JHH = 8.1), 7.13 d.d (2H, C3H,
C5H, 3JHH = 7.8, 3JHH = 8.1); the phosphoryl fragment:
7.48 m (6H, 2C3H, 2C4H, 2C5H), 7.71 m (2H, C2H,
C6H), 7.87 m (2H, C2'H, C6'H).
5.58 m (2H, NH, N–CH–P); the furan fragment: 4.14
m (2H, CH2OH), 4.94 br.s (1H, CH2OH), 6.42 m (2H,
C4H, C3H); the phenylhydrazine fragment: 6.78 d (2H,
3
3
C2H, C6H, JHH = 7.8), 6.97 d (1H, C4H, JHH = 8.1),
Ethyl[hydroxylamino-(5-hydroxymethyl-2-furyl)-
7.13 d.d (2H, C3H, C5H, JHH = 7.8, JHH = 8.1); the
phosphoryl fragment: 7.57 m (6H, 2C3H, 2C4H,
2C5H), 7.75 t (2H, C2H, C6H, 3JHP = 10.5), 7.80 t (2H,
C2'H, C6'H, 3JHP = 11.3).
3
3
methyl]phenylphosphinate (IIf). Yield 0.12 g (28%).
1
Syrup. [α]D = 0. H NMR spectrum, δ, ppm: 5.56 m
(2H, NH, N–CH–P); the furan fragment: 4.16 m (2H,
CH2OH), 4.98 br.s (1H, CH2OH), 6.46 m (2H, C4H,
C3H); the aminophosphoryl fragment: 5.67 br.s (1H,
NH), 6.42 br.s (1H, OH), 7.52 m (6H, 2C3H, 2C4H,
N-[(Diphenylphosphoryl)(furan-2-yl)methyl]hyd-
roxylamine (IIc). Yield 0.15 g (47%). Syrup. [α]D
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

HYDROPHOSPHORYLATION OF MONOSACCHARIDES OXIMES
1629
2C5H), 7.76 m (2H, C2H, C6H), 7.83 m (2H, C2'H,
C6'H).
evaporator, the product was dried at a temperature of
55°C in a vacuum (12 mm Hg) for 6 hours. Yield 2.00 g
(74%). Rf 0.42. Syrup. [α]D = –5.6. 1H NMR spectrum,
δ, ppm, J, Hz: glycone, 1.38, 1.43, 1.45, 1.55 4C (12H,
1-C-Diphenylphosphoryl-1-deoxy-1-hydroxylamino-
D-sorbitol (III). 1 mmol (0.195 g) of glucose oxime
and 1 mmol (0.202 g) of diphenylphosphosphinous
acid were dissolved in 5 ml of DMF saturated with
argon. The reaction mixture was stored at room
temperature for 48 h, then DMF was removed on a
rotary evaporator, the residue was dissolved in
ethanol:chloroform 3: 1 mixture, filtered through 5 cm
layer of silica gel on a column of 1 cm diameter, then
silica gel was washed twice with 10 ml of the same
mixed solvent, the solution was evaporated to dryness,
the residue was dried in a vacuum (12 mm Hg)at 70°C
for 6 h. Yield 0.14 g (36%). Syrup. [α]D = +3.6. 31P
3
3
CH3), 3.48 m [1H, C4H, JHH(3) = 2.6, JHH(5) = 7.3],
4.10 d [2H, C6H, C6'H, 3JHH(5) = 6.0], 4.40 m [1H, C5H,
3
3JHH(4) = 7.3, JHH(6,6') = 6.0], 4.51 br (1H, C4OH), 4.78
3
3
m [1H, C2H, JHH(3) = 6.0], 4.91 m [1H, C3H, JHH(2)
=
6.0, 3JHH(4) = 2.6], 7.46 m (1H, C1H); aglycone: 6.94 m
(3H, C2H, C4H, C6H), 7.21 m (2H, C3H, C5H, JHH
=
3
8.8), 7.75 br (1H, N–NH). Found, %: C62.18, 62.09; N
6.89, 6.95; N 7.42, 7.54. Calculated, %: C18H26N2O5. C
61.70; N 7.48; N 7.99.
Phenylhydrazones Va, Vb (general procedure).
0.01 mol of phenylhydrazone Ia, Ib was dissolved in
5 ml of anhydrous pyridine, then at stirring and cooling
to 0–5°C was added 0.072 mol (6.8 ml, 7.34 g) of
acetic anhydride, the mixture was stirred for 2 h at this
temperature and then for 2 h at room temperature. The
solution was concentrated in a vacuum and the residue
was chromatographed. The solvents were removed in a
vacuum, the product was dried at 55°C in a vacuum
(12 mm Hg) for 6 h.
1
NMR spectrum, δP, ppm: 32.1. H NMR spectrum, δ,
ppm, J, Hz: the carbohydrate fragment, 3.59 m (1H,
3
C2H), 4.01 m [1H, C4H, JHH(3) = 6.0], 4.26 m (3H,
C5H, C6H, C6'H), 4.43 m [1H, C3H, 3JHH(4) = 6.0], 5.52 m
2
(1H, C1H, JHP = 12.6); the aminophos-phoryl
fragment: 6.13 br. s (1H, OH), 6.64 br.s (1H, NH),
7.54 m (6H, 2C3H, 2C4H, 2C5H), 7.77 m (2H, C2H,
3
3
C6H, JHP = 10.7), 7.88 m (2H, C2'H, C6'H, JHP
=
10.7). Found, %: C54.15, 54.17; H 6.13, 6.20; N 3.17,
3.19; P 8.08, 8.03. Calculated, %: C18H24NO7P.
C54.41; H 6.09; N 3.52; P 7.79.
N-(2,3,4,5-Tetra-O-acetyl-D-xylosyl)-N'-phenyl-
hydrazine (Va). Yield 2.15 g (53%). Syrup. Rf 0.7.
[α]D = –4.0. H NMR spectrum, δ, ppm, J, Hz:
1
N-(2,3;5,6-Di-O-isopropylidene-β-D-mannofurano-
zyl)hydroxylamine (IVa) was obtained employing the
procedure in [22] from 2.6 g of 2,3;5,6-di-O-
isopropylidene-β-D-mannofuranose and 7.5 g of hyd-
roxylamine hydrochloride. Yield 1.60 g (69%). mp
glycone, 2.10–2.15 m [12H, 4C(O) OCH3], 4.05 m
3
3
[1H, C4H, JHH(5) = 8.4, JHH(3) = 9.2], 4.24 m (2H,
C5H, C5'H), 5.46 m (2H, C3H, C2H), 7.44 m (1H, C1H);
3
aglycone: 6.82 d (2H, C2H, C6H, JHH = 7.5), 6.97 d
(1H, C4H, 3JHH = 7.6), 7.23 d.d [2H, C3H, C5H, 3JHH(2,6)
7.5, JHH(4) = 7.6]. Found, %: C55.92, 55.93; H 5.73,
5.76; N 6.54, 6.60. C19H24N2O8: Calculated, %:
C55.88; H 5.92; N 6.86.
=
1
3
156–158°C (published data: 137–138°C). Rf 0.28. H
NMR spectrum, δ, ppm, J, Hz: glycone, 1.35, 1.40,
1.42, 1.52 4C (12H, CH3), 3.68 br.s (1H, C4H), 4.05 m
(1H, C5H), 4.15 m (2H, C6H, C6H (), 4.33 br (1H, C4
3
3
OH), 4.57 d.d [1H, C3H, JHH(2) = 7.7, JHH(4) = 0.9],
N-(2,3,4,5,6-Penta-O-acetyl-D-glyucosyl])-N'-phe-
nylhydrazine (Vb). Yield 2.71 g (56%). Syrup. Rf 0.7.
5.25 d.d [1H, C2H, JHH(1) = 3.4, JHH(3) = 7.7], 7.11 d
3
3
1
[1H, C1H, JHH(2) = 3.7]; aglycone: 9.53 br (1H, N–
3
[α]D = –4.0. H NMR spectrum, δ, ppm, J, Hz:
glycone, 2.04–2.08 m [15H, 5C(O)OFCH3], 4.09 m
OH). Found, %: C53.28, 53.30; H 7.65, 7.63; N 5.22,
5.17. Calculated, %: C12H21NO6. C 52.35; N 7.69; N
5.09.
3
3
[1H, C4H, JHH(5) = 9.0, JHH(3) = 13.2], 4.24 m (2H,
C6H, C6'H), 5.15 m [1H, C5H, JHH(4) = 9.0], 5.51 m
3
(2H, C3H, C2H), 7.46 m (1H, C1H); aglycone: 6.86 d
(2H, C2H, C6H, JHH = 7.3), 6.98 d (1H, C4H, JHH
=
=
N-(2,3;5,6-Di-O-isopropylidene-β-D-mannofurano-
zyl)-N'-phenylhydrazine (IVb). 0.01 mol (2.6 g)
2,3;5,6-di-O-isopropilidenmannoze was dissolved in
20 ml of ethanol, 0.0005 mol (0.03 g, 0.029 ml) of
glacial acetic acid was added, then at stirring 0.011 mol
(1.19 g) of phenylhydrazine was added. Reaction
mixture was stirred at 55°C for 4 h, the solution was
then concentrated in a vacuum, and the residue was
chromatographed. Solvents were removed on the rotary
3
3
7.7), 7.21 d.d [2H, C3H, C5H, JHH(2,6) = 7.3, JHH(4)
3
3
7.7]. Found, %: C56.12, 56.10; H 6.03, 5.99; N 5.65,
5.67. C22H28N2O10. Calculated, %: C55.70; H 5.87; N
5.83.
Compounds VIa–VIf (general procedure). To 1 mmol
of a derivative IV, Va, Vb and 1 mmol of
diphenylphospinous acid or phenyl phenylphosphonite
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1630
BOBRIKOVA et al.
dissolved in 5 ml of chloroform saturated with argon
was added 0.05 mmol (3.9 mg, 0.004 ml) of pyridine.
The solution was placed into an ampule, the ampoule
was sealed and then was heated for 6 h (in the case of
compounds VIa, VIc,VId) or for 12 h (compounds
VIb, VIe, VIf) at 85°C (in the bath). At the end of
reaction, chloroform was distilled off on the rotary
evaporator and the residue was chromatographed. The
solvent was evaporated and the product was dried at
65°C in a vacuum (12 mm Hg) for 6 h.
fragment: 5.68 br.s (1H, NH), 6.20 br.s (1H, OH), 7.53
m (6H, 2C3H, 2C4H, 2C5H), 7.74 m (2H, C2H, C6H),
7.87 m (2H, C2'H, C6'H).
1-C-Diphenylphosphoryl-1-deoxy-1-(phenylhyd-
razino)-2,3,4-tri-O-acetyl-D-xylitol (VId). Yield 0.29 g
(49%). Syrup. Rf 0.20. [α]D +7.6. 1H NMR spectrum, δ,
ppm, J, Hz: the carbohydrate fragment: 1.96–2.08 m
(18H, 3C(O)CH3, [3C(O)CH3]), 3.79 m {2H, C5H,
[C5H], 3JHH(4) = 5.2}, 3.87 m {2H, C5'H, [C5'H], 3JHH(4)
=
3
5.2}, 4.90 m {2H, C2H, [C2H], JHH(1) = 8.4}, 4.93 m
3
{2H, C4H, [C4H], JHH(5,5') = 5.2}, 5.35 m (2H, C3H,
1-C-Diphenylphosphoryl-1-deoxy-1-(hydroxyl-
amino)-2,3;5,6-di-O-isoropylidene-D-mannitol (VIa).
Yield 0.26 g (55%). mp 104–106°C. Rf 0.25. [α]D =
–26.4. 1H NMR spectrum, δ, ppm, J, Hz: the
carbohydrate fragment: 1.27–1.74 m (12H, CH3), 3.69
br.s (1H, C4H), 4.08 m (1H, C5H), 4.19 m (2H, C6H,
C6'H), 4.40 br.s (1H, C4OH), 4.64 m (1H, C3H), 5.25 m
3
2
[C3H]), 5.59 m {2H, C1H [C1H], JHH(2) = 8.4, JHP
=
12.9}; the phenylhydrazine fragment: 6.73 d (2H, C2H,
C6H, JHH = 7.7), [6.80 d (2H, C2H, C6H, JHH = 7.7)],
3
3
6.94 d (1H, C4H, 3JHH = 8.5), [7.03 d (1H, C4H, 3JHH
=
8.3)], 7.13 d.d (2H, C3H, C5H, JHH = 7.7, JHH = 8.5),
3
3
[7.17 d.d (2H, C3H, C5H, JHH = 7.7, JHH = 8.3)]; the
phosphoryl fragment: 7.52 m (6H, 2C3H, 2C4H,
2C5H), 2 C5H), [7.62 m (6Н, 2 C3H, 2 C4H, 2 C5H)],
3
3
2
(1H, C2H), 7.38 m (1H, C1H, JHP = 13.0); the
aminophosphoryl fragment: 5.89 br.s (1H, NH), 6.62
br.s (1H, OH), 7.54 m (6H, 2C3H, 2C4H, 2C5H), 7.73
7.81 m (4Н, 2C2H, 2C6H, JН,Р = 11.1), [7.99 m (4Н,
3
3
m (2H, C2H, C6H, JHP = 11.3), 7.87 m (2H, C2'H,
2C2'H, 2C6'H, 3JНР = 11.1)].
C6'H, 3JHP = 11.2).
1-C-Diphenylphosphoryl-1-deoxy-1-phenylhyd-
razino-2,3,4,6-tetra-O-acetyl-D-sorbitol (VIe). Yield
1-C-Diphenylphosphoryl-1-deoxy-1-(phenylhyd-
razino)-2,3;5,6-di-O-isopropylidene-D-mannitol (VIb).
1
0.36 g (53%). Syrup. Rf 0.18. [α]D = +9.1. H NMR
1
Yield 0.29 g (52%). Syrup. Rf 0.19. [α]D = –20.3. H
spectrum, δ, ppm, J, Hz: the carbohydrate fragment:
1.90–2.10 m (24H, 4C(O)CH3, [4C(O)CH3]), 4.08 m
(4H, C6H, C6'H, [C6H, C6'H]), 4.24 m (2H, C5H,
[C5 H]), 4.86 m (2H, C4H, [C4H]), 4.98 m (2H, C3H,
NMR spectrum, δ, ppm, J, Hz: the carbohydrate
fragment: 1.31–1.85 m (24H, CH3), 3.78 m (2H, C4H,
[C4H]1), 4.04 m (2H, C5H, [C5H]), 4.16 m (4H, C6H,
C6'H, [C6H, C6'H]), 4.45 m (2H, C4OH, [C4OH]), 4.63
m (2H, C3H, [C3H]), 5.25 m (2H, C2H, [C2H]), 7.44 m
3
2
[C3H]), 5.26 m (2H, C1H, [C1H], JHH(2) = 5.8, JHP
=
12.7), 5.54 m {2H, C2H, [C2H], JHH(1) = 5.8}; the
3
2
(2H, C1H, [C1H], JHP = 12.8); the phenylhydrazine
phenylhydrazine fragment: 6.71 d (2H, C2H, C6H, 3JHH
=
3
3
fragment: 6.78 d (2H, C2H, C6H, JHH = 7.8), [6.86 d
7.5), [6.81 d (2H, C2H, C6H, JHH = 7.6)], 6.97 d (1H,
3
3
3
3
(2H, C2H, C6H, JHH = 7.8)], 6.97 d (1H, C4H, JHH
=
C4H, JHH = 8.4), [7.02 d (1H, C4H, JHH = 8.2)], 7.10
8.1), [7.02 d (1H, C4H, 3JHH = 8.1)], 7.13 d.d (2H, C3H,
C5H, 3JHH = 7.8, 3JHH = 8.1), [7.17 d.d (2H, C3H, C5H,
3JHH = 7.8, 3JHH = 8.1)]; the phosphoryl fragment: 7.56
m (12H, 2C3H, 2C4H, 2C5H, [2C3H, 2C4H, 2C5H]),
d.d (2H, C3H, C5H, JHH = 7.5, JHH = 8.4), [7.19 d.d
3
3
3
3
(2H, C3H, C5H, JHH = 7.6, JHH = 8.2)]; the
phosphoryl fragment: 7.51 m (6H, 2C3H, 2C4H,
2C5H), [7.63 m (6H, 2C3H, 2C4H, 2C5H)], 7.88 m (4H,
7.84 m (4H, C2H, C6H, [C2H, C6H], JHP = 10.6), 7.92
2C2H, 2C6H, JHP = 12.6), [8.08 m (4H, C2'H, C6'H,
3
3
m (4H, C2'H, C6'H, [C2'H, C6'H], 3JHP = 10.8).
3JHP = 12.5)].
1-Deoxy-1-C-phenylphenoxyohosphoryl-1-hyd-
roxylamino-2,3;5,6-di-O-isopropylidene-D-mannitol
(VIc). Yield 0.17 g (35%). Syrup. Rf 0.28. [α]D = –28.6.
1H NMR spectrum, δ, ppm, J, Hz: the carbohydrate
fragment: 1.12–1.56 m [12H, 2C(CH3)2], 3.83 m [1H,
1-Deoxy-1-C-phenylphenoxyphosphoryl-1-phenyl-
hydrazino-2,3,4,6-tetra-O-acetyL-D-sorbitol (VIf).
Yield 0.23 g (36%). Syrup. Rf 0.25. [α]D = –13.6. H
1
NMR spectrum, δ, ppm, J, Hz: the carbohydrate
fragment: 1.62–2.04 m [12H, 4C(O)CH3], 4.06 m (2H,
C6H, C6'H), 4.16 m (1H, C5H), 4.78 m (1H, C4H), 4.86
br.s (1H, OH), 5.18 m (1H, C3H), 5.59 m [1H, C2H,
3
C4H, JHH(5) = 5.5], 4.06 m (2H, C6H, C6'H), 4.26 m
(1H, C5H), 4.47 m (1H, C3H); 4.76 m (1H, C2H), 5.17
2
3
m (1H, C1H, JHP = 12.8); the aminophosphoryl
3JHH(1) = 5.2], 5.78 m [1H, C1H, JHH(2) = 5.2]; the
phenylhydrazine fragment: 6.73 d (2H, C2H, C6H,
3JHH = 7.8), 7.08 d (1H, C4H, 3JHH = 8.6), 7.19 d.d (2H,
1
In the brackets are given the values of chemical shifts and spin–
3
3
C3H, C5H, JHH = 7.8, JHH = 8.6); the phosphoryl
spin coupling constants of the second diastereomer.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

HYDROPHOSPHORYLATION OF MONOSACCHARIDES OXIMES
1631
fragment: 7.49 m (6H, 2C3H, 2C4H, 2C5H), 7.75 m
(2H, C2H, C6H), 7.93 m (2H, C2'H, C6'H).
15. Huber, R., Knierzinger, A., Obrecht, J.-P., and Vasella, A.,
Helv. Chim. Acta, 1985, vol. 68, no. 6, p. 1730.
16. Hassen, Z., Ben Akacha, A., and Hajjem, B., J. Fluorine
Chem., 2003, vol. 121, no. 2, p. 177.
17. Palacios, F., Aparicio, D., Lupez Y., and de los San-
tos, J.M., Tetrahedron Lett., 2004, vol. 45, no. 22, p. 4345.
18. Davis, B.G., J. Chem. Soc., Perkin Trans. 1, 1999,
no. 22, p. 3215.
19. Romeo, G., Iannazzo, D., Piperno, A., Romeo, R.,
Corsaro, A., Rescifina, A., and Chiacchio, U., Mini-Rev.
Org. Chem., 2005, vol. 2, no. 1, p. 59.
20. Lantos, I., Flisak, J., Liu, L., Matsuoka, R., Mendelson, W.,
Stevenson, D., Tubman, K., Tucker, L., Zhang, W.-Y.,
Adams, J., Sorenson, M., Garigipati, R., Erhardt, K.,
and Ross, S., J. Org. Chem., 1997, vol. 62, no. 16, p. 5385.
21. Basha, A., Henry, R., McLaughlin, M.A., Ratajczyk, J.D.,
and Wittenberger, S.J., J. Org. Chem., 1994, vol. 59,
no. 20, p. 6103.
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