Synthesis of the novel β-aminophosphoryl compounds and their acid-base properties and membrane-transport abilities towards carboxylic acids

Article abstract of DOI:10.1007/s11172-012-0024-7

The highly efficient synthesis of β-aminophosphoryl compounds with one and two ethyl- phosphoryl groups was performed by the addition of amines to the vinylphosphoryl compounds in water as a solvent. The acid-base properties and membrane-transport abiliti

Full text of DOI:10.1007/s11172-012-0024-7

Russian Chemical Bulletin, International Edition, Vol. 61, No. 1, pp. 174—180, January, 2012
174
Synthesis of the novel ꢀaminophosphoryl compounds and their acidꢀbase
properties and membraneꢀtransport abilities towards carboxylic acids
R. A. Cherkasov,a A. R. Garifzyanov,a N. V. Kurnosova,a E. V. Matveeva,b and I. L. Odinetsb
aKazan (Volga Region) Federal University,
18 ul. Kremlevskaya, 420008 Kazan, Russian Federation.
Eꢀmail: rafael.cherkasov@ksu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Eꢀmail: odinets@ineos.ac.ru
The highly efficient synthesis of ꢀaminophosphoryl compounds with one and two ethylꢀ
phosphoryl groups was performed by the addition of amines to the vinylphosphoryl comꢀ
pounds in water as a solvent. The acidꢀbase properties and membraneꢀtransport abilities of the
target compounds towards carboxylic acids were studied. Selectivity towards acetic acid was
revealed.
Key words: ꢀaminophosphonates, ꢀaminophosphine oxides, green chemistry, reactions
in water, acidꢀbase properties, membraneꢀtransport properties, carboxylic acids.
Pronounced interest appeared in recent decades in the
their possible use for the development of selective ionoꢀ
phores and membrane carriers.9
development of synthesis methods and investigation of the
properties of ꢀaminophosphoryl compounds is caused by
a wide scope of practically useful compounds of this type.
Being analogs of natural amino acids, they possess diverse
biological activity, the type of which is determined by both
the linker length and the environment of the nitrogen and
phosphorus atoms, and serve as objects of intensive studꢀ
ies of both synthetic chemists and specialists in the areas
of biochemistry, pharmaceutics, medicine, agriculture,
and other related disciplines.1—3
The corresponding ꢀaminophosphonates and their deꢀ
rivatives, among which the substances were revealed that
exhibit antibacterial, antiviral, and antifungal activities and
properties of inhibitors of metalloproteases, growth facꢀ
tors, etc.,3 have been studied in most detail to the present
time. The aminophosphoryl framework of these moleꢀ
cules combines the phosphoryl and amine functional
groups, which are responsible for the manifestation of
complexation properties predetermining the possibility
of their use as liquid and membrane extracting agents
for objects of various nature: organic and inorganic acids
and alkaline, alkalineꢀearth, rare, scattered, and noble
metals.4—7
In the present work, we synthesized novel ꢀaminoꢀ
phosphoryl compounds with one (1—5) and two (6 and 7)
ꢀethylphosphoryl groups containing the secondary or terꢀ
tiary nitrogen atom in order to study the acidꢀbase properꢀ
ties and membraneꢀtransport abilities of the ꢀaminophosꢀ
phoryl compounds towards acidic substrates, viz., carbꢀ
oxylic acids with different structures (monobasic acetic
and dibasic oxalic and tartaric acids containing several
protonꢀdonor groups), which could predetermine variety
of possibilities of their binding with carrier molecules. Their
ꢀanalogs were also used for comparison: phosphine
oxide (8) and phosphonate (9) containing the highly
lipophilic nꢀoctyl groups at potential coordination sites
(nitrogen and phosphorus atoms).
The optimum in terms of simplicity method for the
synthesis of ꢀaminophosphonates is the addition of
amines to the terminal bond of vinyl phosphonates,10—12
which is usually carried out under rather drastic condiꢀ
tions (prolong heating in the presence of amine excess, the
use of the basic catalysts, etc.). We have recently shown13—15
that the use of water as a solvent (in the absence of any
organic cosolvent or catalyst) substantially increases the
rate of this reaction, giving the target products in yields
close to quantitative. Both waterꢀsoluble (diethyl vinylꢀ
phosphonate)13 and insoluble in water (diphenylvinylphosꢀ
phine oxide)14,15 organophosphorus substrates can be used
in the reaction, and the decrease in the reaction rate can
be compensated by an elevated temperature (100 С),
At the same time, the study of the properties of the
ꢀaminophosphoryl compounds related in structure has
not attracted considerable attention up to presently,
although a series of similar compounds also exhibit a broad
spectrum of biological activity8 and their complexation
ability towards a wide series of metal ions forms a basis for
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 171—177, January, 2012.
1066ꢀ5285/12/6101ꢀ174 © 2012 Springer Science+Business Media, Inc.

ꢀAminophosphoryl compounds
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
175
which does not result in any secondary interactions. Unꢀ
like the classical conditions of this reaction, the use of
water corresponding to all principles of green chemistry
makes it possible to perform easily the double phosphonoꢀ
ethylation of primary amines to form bis(ꢀethylphosꢀ
phoryl)amines when using stoichiometric ratios of the
reactants.
Therefore, the novel ꢀaminophosphoryl compounds
were synthesized in water as a solvent. Although the reacꢀ
tion rate for dibutyl vinylphosphonate is somewhat lower
than that for its analog with the ethoxy groups at the phosꢀ
phorus atom,13 the addition of hexylamine and octylamine
(compounds 2 and 3) proceeds smoothly at ambient temꢀ
perature (Scheme 1). At the same time, it is reasonable to
perform the reaction on heating at a decrease in the soluꢀ
bility of one of the reactants, for example, when dioctylꢀ
amine (compounds 4 and 5) or diphenylvinylphosphine
oxide (compounds 1 and 5) is used and when double
phosphonoethylation (compounds 6 and 7) is carried out.
In most cases, the products were isolated by lyophilic dryꢀ
ing, whereas additional purification by flash chromatoꢀ
graphy was required for compounds 4 and 7.
with  ~31 characteristic of this type of environment of the
1
phosphorus atom. The H and 13С NMR spectra comꢀ
pletely correspond to the structure of the synthesized comꢀ
pounds and contain the signals of the protons and carbons
of the PCH2 and NCH2 groups, respectively, in addition
to the characteristic groups of signals of the corresponding
substituents at the phosphorus and nitrogen atoms.
When estimating the efficiency of membrane transport
of proton substrates, important information can be obꢀ
tained by comparing the values of transfer flows and acidꢀ
base properties of carrier molecules. For a large array
of the ꢀaminophosphoryl compounds, we determined
the acidic dissociation rate constants of the conjugated
acids in a medium of aqueous propanꢀ2ꢀol16—19 and, for a
few number of examples, respective constants of their
ꢀaminophosphoryl analogs were determined.11 A comꢀ
parison of the obtained values of рКа with the correspondꢀ
ing values for the amineꢀprecursors showed that ꢀphosꢀ
phorylamines exceed in basicity the ꢀderivatives with simꢀ
ilar structure by 2—3 рКа units, on the average, and are
inferior by 4—5 рКа units to the corresponding amines.
A similar decrease in basicity was explained by a strong
acceptor influence of the phosphoryl group situated through
two or one carbon atom, respectively, from the basic site,
nitrogen atom.
Scheme 1
The рКа values of the aminophosphoryl compounds
used in this work were determined by potentiometric titraꢀ
tion according to a described procedure20; their values are
given in Table 1.
As can be seen from the data in Table 1, the earlier
observed regularities of changing the рКа values of the
conjugated acids, their dependence on the distance beꢀ
tween the phosphoryl group and the protonꢀacceptor site
(nitrogen atom) are manifested in this experiment: the
basicity of ꢀphosphorylamines 1—3 is almost indepenꢀ
dent of the nature of substituents at the phosphorus atom
and exceeds the same value for the ꢀanalogs by 2—4 рКа
units. A fairly sharp decrease in the basicity of diphosphoꢀ
rylated amines 6 and 7 also fits well with the general tenꢀ
dency: the introduction of the second acceptor phosphorꢀ
yl group more strongly decreases the electron density on
the nitrogen atom. Note that the decrease in the basicity
in ,ꢀbis(dialkylphosphorylmethyl)amines is so high that
their values are below the limits of experimental determiꢀ
nation (рКа < 2).18 Naturally, two dialkoxyphosphoryl
groups arranged by one methylene fragment farther from
the nitrogen atom (6 and 7) exert a smaller electronꢀacꢀ
ceptor effect on the basic site, decreasing, nevertheless,
the values of рКа by 2—3 units compared to ꢀmonophosꢀ
phorylated amines.
R1 = Ph, R2 = C6H13, R3 = H (1); R1 = OBu, R2 = C6H13
,
R
R
3 = H (2); R2 = C8H17, R3 = H (3); R2 = R3 = C8H17 (4);
1 = Ph, R2 = R3 = C8H17 (5); R1 = OBu (6), OEt (7)
The compositions and structures of the synthesized
compounds were confirmed by the elemental analysis,
IR spectroscopy, and multinuclear NMR spectroscopy
data. According to the elemental analysis data, compound 5
is a stable hemihydrate. The IR spectra of ꢀaminophosꢀ
phoryl compounds 1—7 contain the characteristic absorpꢀ
tion bands of the phosphoryl group at 1237—1248 and
1180—1184 cm–1 for phosphonates and phosphine oxide,
respectively. The 31Р NMR spectra exhibit singlet signals
The values of рКа of preceding amine determined by us
under the same conditions as the acidic dissociation of
phosphorylamines (water—propanꢀ2ꢀol (1 : 1), 25 С),
were 9.49, 8.98, and 9.68 for octylamine, dioctylamine,
and hexylamine, respectively; i.e., the difference in basicꢀ

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Cherkasov et al.
Table 1. Characterization of the acidꢀbase and membraneꢀtransport properties of the aminophosphoryl compounds
Transfer flow,b T•106/mol m–2 min–1
a
Aminophosphoryl compound
рКа
Acetic acid
Oxalic acid
Tartaric acid
7.46
1.40
6.00
3.04
<10–7
7.33
7.37
0.29
8.17
<10–7
10.20
<10–7
5.83
6.15
267.90
77.50
0.51
148.6
32.67
104.17
1.83
4.45
4.81
1.97
0.25
<10–7
d
—
<10–7
c
5.23
3.68
872.00
153.26
—
<10–7
<10–7
52.15
а Constant for the aminophosphoryl compounds.
b The concentration of the carrier in the membrane phase is 0.2 mol L–1, and the substrate concentration is 0.2 mol L–1
c Forms a complex insoluble in the membrane.
d Washed out of the membrane.
.
ity of ꢀphosphorylamines and their amineꢀprecursors was
2—4 рКа units for monoꢀ (1—5) and 4—5 рКа units for diꢀ
(phosphorylethyl)amines 6 and 7. This is well consistent
with the earlier revealed and above discussed regularities.
Note that the results obtained explain the possibility of
occurrence of double phosphonoethylation in water, where
Nꢀnucleophiles with рКа higher than 6 easily enter the
reaction. In other words, the formed products with one
ethylphosphoryl group are appropriate as Nꢀnucleophiles
for the reaction under these conditions. In addition, the
difference in the basic properties of the primary amines
and their ꢀaminophosphoryl derivatives reasonably exꢀ

ꢀAminophosphoryl compounds
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
177
plains the reaction of double phosphonoethylation as
a stepꢀbyꢀstep process, where the ꢀaminophosphoryl
product that formed cannot compete with the primary
amine as an Nꢀnucleophile.
ic substrates through liquid impregnated membranes. The
experimental method and its mathematical processing are
similar to those described earlier.22 Phenylcyclohexane was
chosen as a membrane medium, since this solvent is highly
boiling and indifferent to molecules of substrates and carꢀ
riers and provide stable conditions of measuring the values
of transfer flows.
The literature23 and our earlier24 data on the mechaꢀ
nism of membrane transport of the protonꢀdonor subꢀ
strates by the neutral phosphoryl and amine carriers indiꢀ
cate in favor of the solvate mechanism, which assumes the
membrane extraction of carboxylic acid by the aminoꢀ
phosphoryl reactants in the form of Hꢀcomplexes, and it
is the nitrogen atom that acts as the protonation site. It is
natural to assume that the transfer of the chosen acids
by the ꢀaminophosphoryl reactants also occurs with
the preliminary formation of the Hꢀcomplex of the
O=PCH2CH2N···H—A type, the easiness of formation of
which depends on the basicity of the amine center and the
strength of the transferred acid.
However, as we indicated several times,22,24 the atꢀ
tempts to reveal rather simple interrelations of the strucꢀ
tures of the carrier and substrate, on the one hand, and the
values of transfer flows (transfer efficiencies), on the other
hand, are unsuccessful, as a rule. This is related to the
influence of many, often mutually compensating factors
on the efficiency. The value of the transfer flow depends,
obviously, on the binding rate of the carrier with the subꢀ
strate and on the easiness of reꢀextraction in the accepting
phase. In addition, in polyfunctional complexing agents
of the type of the aminophosphoryl compounds studied by
us, not all but these or other coordination sites (for example,
for steric reasons) can participate in binding with the transꢀ
ferred substrate. One of the important factors can be
a change in the viscosity of the membrane phase with
changing the concentration and nature of the transferred
complex and some other hardly taken into account charꢀ
acteristics of the process and its participants.25,26 Howevꢀ
er, as shown, in particular, by the results of the present
study, the hydrophilic (lipophilic) characteristics of the
extracting agent are among the most significant parameꢀ
ters determining the interfacial transfer rate; i.e., we speak
about such a hardly expressed characteristic as hydroꢀ
philic—lipophilic balance.
The difference in the values of basicity of secondary
(1—3) and tertiary (4 and 5) phosphorylated amines is
significant and also obvious for the comparison of рКа of
their ꢀanalogs 8 and 9. A similar phenomenon has earlier
been observed16 for many examples in the structural analogs
of ꢀaminoethyl phosphonates studied in this work, viz.,
ꢀaminoalkyl phosphonates and ꢀphosphine oxides. This
phenomenon was explained assuming that the intramoꢀ
lecular Hꢀcomplexes N—H···O=P are involved in the acidꢀ
base equilibria of secondary phosphorylamine molecules.
It is most likely that this effect takes place in the series of their
ꢀanalogs as well. It can be assumed that the thermodyꢀ
namically favorable formation of the sixꢀmembered ring
predetermines the affinity of secondary ꢀphosphorylꢀ
amines to intramolecular hydrogen bonding to complex А.
Indeed, the identical character of the IR spectra of
compound 2, in particular, the absorption bands of the
P=O group at 1246 cm–1 and the broad adsorption NН
band at 3306 cm–1 in thin layer and in СCl4 solutions (at
different dilutions) indicate that the molecule includes the
intramolecular hydrogen bond with the formation of the
sixꢀmembered Hꢀring. The absorption bands of the unꢀ
bound groups, P=O and NH, are absent from the spectra.
Nevertheless, it should be mentioned that in crystal of the
single structurally characterized ꢀaminophosphoryl comꢀ
pound, [2ꢀ(tertꢀbutylamino)ethyl]diphenylphosphine oxꢀ
ide [ButNH(CH2)2P(O)Ph2], the molecules are bound by
strong intermolecular hydrogen bonds P(O)...H—N(But)
involving the phosphoryl oxygen atom.21
Evidently, the protonated form of ꢀphosphorylamines
is able to Hꢀcomplexation by type B; however, the formaꢀ
tion of this Hꢀcomplex requires the conformational tranꢀ
sition of transꢀform C, in which the phosphorylamine molꢀ
ecules exist due to the repulsion of the strong PO and
CN dipoles,16 to the cisꢀconformation favorable for the
formation of the sixꢀmembered ring in complex B. It is
most likely that the energy of transformation of the neuꢀ
tral molecule of tertiary phosphine to the intramolecular
Hꢀcomplex of conjugated acid C affects the differences in
basicity of secondary and tertiary amines. However, the
role of other factors cannot be excluded, for example, hyꢀ
drophobic interactions of bulky substituents or solvation
of the protonation sites differed by steric characteristics.
We have previously shown16 using the correlations that
only the aminophosphoryl compounds, whose molecules
contain at least 20 carbon atoms, can serve as efficient
liquid and membrane extracting agents. In this case, the
interfacial partition coefficient in water—organic solvent
systems exceeds six logarithmic units and, hence, losses of
the transfer due to its retention in the aqueous phase can
be avoided.
An analysis of the values of transfer flows of carboxylic
acids by the aminophosphoryl carriers of different strucꢀ
ture presented in Table 1 revealed no explicit dependence
We studied the possibility of using the newly syntheꢀ
sized aminophosphoryl compounds for the transfer of acidꢀ

178
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Cherkasov et al.
in phenylcyclohexane were used as impregnated membranes.
The initial concentration of carboxylic acids in the donating
solution and the concentration of carriers in the membrane phase
were 0.1 mol L–1. The computer processing of analytical data
was performed using the VisualBasic original program develꢀ
oped by us at the Kazan (Volga Region) Federal University.
The synthesis method and physicochemical characteristics
of Nꢀoctyl(dioctylmethyl)phosphine oxide (8) have been deꢀ
scribed earlier.22
ꢀAminophosphoryl compounds 1—7 (general procedure).
A stoichiometric amount of diphenylvinylphosphine oxide or
diethyl or dibutyl vinylphosphonate (1 mmole for the synthesis
of compounds 1—5 or 2 mmoles in the case of compounds 6 and 7)
was added to a solution of the corresponding amine (1 mmol) in
water (2 mL) at ~20 C. The reaction mixture was stirred for
an indicate time interval at ~20 or 100 С (see further). After
the end of the reaction, the solvent was removed in vacuo. After
lyophilic drying, compounds 1—3, 5, and 6 had purity >98%
(NMR spectral data). In the case of compounds 4 and 7, adꢀ
ditional purification by column chromatography (SiO2,
CHCl3—EtOH (100 : 3)) was carried out.
of the basicity of the proton acceptor or strength of the
acid. The most efficient membrane extracting agents of
acetic and oxalic acids were those containing longꢀchain
hydrocarbon groups at the nitrogen and phosphorus atoms.
ꢀAminophosphine oxide 8, which is less basic than all
ꢀaminophosphoryl compounds used in the work, deꢀ
monstrates the highest flow value. The significance of the
lipophilic properties of the carrier is also confirmed by a
comparison of the transfer flow values of acids by monoꢀ
and bisphosphorylamines: less basic and more lipophilic
diphosphorylamine 6 noticeably exceeds its monophosꢀ
phorylated analog 2 in transfer efficiency, and the substitꢀ
uents at the nitrogen and phosphorus atoms are the same.
In the general case, the same aminophosphoryl groups
are more active in processes of membrane transport of
monobasic acetic acid than in the case of dibasic oxalic
acid. The probable reason for this difference can be the
nature of Hꢀcomplexes formed by molecules of phosꢀ
phorylamines and carboxylic acids. If assuming that they
include one acid molecule and one amine molecule, the
complex formed by oxalic acid contains the unbound "exꢀ
cessive" carboxyl group well solvated by water molecules
in the donating aqueous phase. In this case, an almost
complete absence of membrane transport by the chosen
tartaric acid becomes clear. Evidently, an excess of hydroꢀ
philic carboxyl and hydroxyl groups in the complexes
formed by tartaric acid results in their strong retention in
the donating aqueous solution. A similar effect was obꢀ
served earlier22,24 when studying the membrane extraction
of carboxylic and hydroxycarboxylic acids by ꢀaminoꢀ
methylphosphine oxides and other functionalized phosꢀ
phoryl reagents.
[2ꢀ(Hexylamino)ethyl]diphenylphosphine oxide (1). Reaction
conditions: 5 h at 100 С. The yield was 91% (after lyophilic
drying), white powder, m.p. 69—71 С. 31P NMR (CDCl3), :
31.35. 1H NMR (CDCl3), : 0.83 (t, 3 H, Me в C6H13, 3JH,H
=
= 6.5 Hz); 1.21 (br.s, 6 H, CH2); 1.34—1.39 (m, 2 H, CH2); 2.06
(br.s, 1 H, NH); 2.47—2.53 (m, 4 H, PCH2 + СН2); 2.91 (quintet,
3
3
2 H, CH2N, JP,H = 10.8 Hz, JH,H = 7.6 Hz); 7.41—7.50,
7.65—7.73 (both m, 6 Н + 4 Н, Ph). 13C NMR (CDCl3), :
13.74 (s, Me); 22.24 (s, CH2); 26.60 (s, CH2); 29.53 (s, CH2);
29.97 (d, PCH2, 1JP,C = 70.8); 31.38 (s, CH2); 42.56 (s, CH2N);
49.39 (s, NCH2 in C6H13); 128.37 (d, mꢀPhP, 3JP,C = 11.6 Hz);
2
4
130.36 (d, oꢀPhP, JP,C = 9.4 Hz); 131.47 (d, pꢀPhP, JP,C
=
:
= 2.6 Hz); 132.66 (d, ipsoꢀC, 1JP,C = 98.9 Hz). IR (KBr), /cm–1
517, 522, 697, 719, 752, 791, 962, 1071, 1103, 1119, 1180 (Р=О),
1436, 1479, 2756, 2805, 2853, 2916, 3295 (NH). Found (%):
C, 72.88; H, 8.69; N, 4.17. C20H28NOP. Calculated (%):
C, 72.92; H, 8.57; N, 4.25.
The selectivity towards acetic acid found by use in the
series of ꢀaminophosphoryl compounds, for instance, of
dibutyl 2ꢀ(dioctylamino)ethylphosphonate 4, suggests that
the compounds of this type can be used for the extraction,
concentrating, and separation of acidic substrates from
natural and technological sources. However, it is evident
that the necessary condition for the efficiency of their use
is the achievement of an optimum hydrophilic—lipophilic
balance by the introduction of the corresponding substituꢀ
ents to the potential coordination sites.
Dibutyl 2ꢀ(hexylamino)ethylphosphonate (2). Reaction conꢀ
ditions: 24 h at 20 С. The yield was 95% (after lyophilic drying),
1
yellow oil. 31P NMR (CDCl3), : 30.66. H NMR (CDCl3), :
3
0.84 (t, 3 H, Me in C6H13, JH,H = 6.7 Hz); 0.91 (t, 6 H, Me,
3JH,H = 7.4 Hz); 1.22—1.29 (m, 6 H, CH2); 1.39 (sextet, 4 H,
3
CH2Me in Bu, JH,H = 7.4 Hz); 1.47 (br.t, 2 H, NCH2CH2 in
C6H13, 3JH,H = 7.0 Hz); 1.61 (quintet, 4 H, OCH2CH2, 3JH,H
=
=
2
3
= 7.4 Hz); 1.98 (dt, 2 H, PCH2, JP,H = 18.2 Hz, JH,H
= 7.3 Hz); 2.58 (t, 2 H, NHCH2 in C6H13, 3JH,H = 7.2 Hz); 2.88
3
3
(quintet, 2 H, CH2N, JP,H = 14.6 Hz, JH,H = 7.3 Hz);
3.95—3.99 (m, 4 H, OCH2). IR (thin layer), /cm–1: 792, 966,
1025 (P—O—C), 1068, 1246 (br, Р=О), 1380, 1467, 2873, 2917,
2951, 3306 (NH), 3439. Found (%): C, 59.79; H, 11.29; P, 9.64.
C16H36NO3P. Calculated (%): C, 59.69; H, 11.44; P, 9.42.
Dibutyl 2ꢀ(decylamino)ethylphosphonate (3). Reaction conꢀ
ditions: 7 days at 20 С. The yield was 98% (after lyophilic dryꢀ
ing), light yellow oil. 31P NMR (CDCl3), : 30.60. 1H NMR
Experimental
NMR spectra were recorded on Bruker AMXꢀ300 and Bruker
AMXꢀ400 spectrometers in CDCl3 solutions using the signal
from residual protons of the deuterated solvent as an internal
standard (for 1Н and 13С, relative to Me4Si) and 85% Н3РО4 as
an external standard for the 31P NMR spectra. IR spectra were
obtained on a MagnaꢀIR 750 FTꢀIR spectrometer (Nicolet) (reꢀ
solution 2 cm–1, number of scans 128, KBr pellets or thin layer).
Acidic dissociation constants were determined by a known
procedure.20 The apparatus and procedure for studying memꢀ
brane transport were described.4 The MFFKꢀ4 filters (Vladipor)
with the pore size 0.6 m impregnated with solutions of carriers
3
(CDCl3), : 0.79 (t, 3 H, Me in C10H21, JH,H = 6.6 Hz); 0.86
3
(t, 6 H, Me, JH,H = 7.4 Hz); 1.18—1.20 (m, 14 H, CH2);
1.31—1.39 (two overlapped m, 4 H + 2 H, CH2Me in Bu and
NHCH2CH2 in C10H21); 1.57 (quintet, 4 H, OCH2CH2, 3JH,H
=
= 6.8 Hz); 1.90 (dt, 2 H, PCH2, 2JP,H = 18.3 Hz, 3JH,H = 7.3 Hz);
3
2.51 (t, 2 H, NCH2 in C10H21, JH,H = 7.2 Hz); 2.81 (quintet,

ꢀAminophosphoryl compounds
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
179
3
3
2 H, CH2N, JP,H = 15.0 Hz, JH,H = 7.2 Hz); 3.90—3.99
(m, 4 H, OCH2). 13C NMR (CDCl3), : 12.08 (s, Me in Bu);
12.57 (s, Me в C10H21); 17.32 (s, CH2Me in Bu); 21.22
(s, CH2Me in C10H21); 24.85 (d, PCH2, 1JP,C = 139.0 Hz); 25.93
(s, CH2); 27.91 (s, CH2); 28.18 (s, 2 CH2); 28.20 (s, 2 CH2);
28.57 (s, CH2); 30.48 (s, NHCH2CH2 in C10H21), 31.19
(d, POCH2CH2, 3JP,C = 5.6 Hz); 41.95 (s, NHCH2 in C10H21);
48.15 (s, CH2N); 63.52 (s, OCH2); 63.58 (s, OCH2). IR (thin
layer), /cm–1: 840, 899, 979, 1025 (P—O—C), 1069, 1243
(P=O), 1379, 1466, 2854, 2926, 2957, 3305 (NH). Found (%):
C, 63.55; H, 11.94; P, 7.95. C20H44NO3P. Calculated (%):
C, 63.63; H, 11.75; P, 8.20.
45.94 (s, CH2N); 52.47 (s, NCH2 in C6H13); 64.66 (s, OCH2);
64.73 (s, OCH2). IR (thin layer), /cm–1: 979, 1024 (P—O—C),
1067, 1238 (br, Р=О), 1381, 1466, 2874, 2933, 2959, 3459 (br,
H2O). Found (%): C, 57.60; H, 10.60; P, 11.21. C26H57NO6P2.
Calculated (%): C, 57.65; H, 10.61; P, 11.44.
N,NꢀDi[2ꢀ(diethoxyphosphoryl)ethyl]hexylamine (7). Reacꢀ
tion conditions: 4 h at 100 С. The yield was 75% (after column
chromatography), light yellow oil. 31P NMR (CDCl3), : 30.70.
1H NMR, : 0.84 (t, 3 H, Me in С6H13
,
3JH,H = 7.0 Hz);
3
1.22—1.24 (m, 6 H, CH2); 1.28 (t, 12 H, Me, JH,H = 7.1 Hz);
1.35—1.38 (m, 2 H, CH2); 1.85 (dt, 4 H, PCH2, 2JP,H = 19.1 Hz,
3JH,H = 7.8 Hz); 2.34 (t, 2 H, NCH2 in С6H13, 3JH,H = 7.0 Hz);
2.72 (quintet, 4 H, CH2N, 3JH,H = 7.8 Hz); 4.00—4.09 (m, 8 H,
OCH2). IR (thin layer), /cm–1: 789, 937, 960, 1032 (P—O—C),
1057, 1248 (br, Р=О), 1392, 1467, 2872, 2932, 2965, 2980.
Found (%): C, 48.35; H, 9.50; P, 13.50. C16H37NO6P2•
•0.2CHCl3. Calculated (%): C, 48.22; H, 9.16; P, 13.66.
Dibutyl 2ꢀ(dioctylamino)ethylphosphonate (4). Reaction conꢀ
ditions: 18 h at 100 С. The yield was 81% (after column chromꢀ
atography), light yellow oil. 31P NMR (CDCl3), : 31.35. 1H
3
NMR (CDCl3), : 0.85 (t, 6 H, Me in C6H13, JH,H = 6.9 Hz);
0.91 (t, 6 H, Me, 3JH,H = 7.5 Hz); 1.24 (br.s, 20 H, CH2); 1.35—1.42
(two overlapped m, 4 H + 4 H, CH2Me in Bu and NCH2CH2 in
C8H17); 1.62 (quintet, 4 H, OCH2CH2, JH,H = 6.7 Hz); 1.87
Dibutyl N,Nꢀdioctylaminomethylphosphonate (9) was syntheꢀ
sized by the Kabachnik—Fields reaction between dibutyl phosꢀ
phite, dioctylamine, and formaldehyde according to the general
3
(dt, 2 H, PCH2, 2JP,H = 19.1 Hz, 3JH,H = 8.0 Hz); 2.35 (t, 4 H,
NCH2 in C8H17, 3JH,H = 7.5 Hz); 2.73—2.79 (m, 2 H, CH2N);
3.95—4.04 (m, 4 H, OCH2). 13C NMR (CDCl3), : 13.27 (s, Me
in Bu); 13.75 (s, Me in C8H17); 18.40 (s, CH2Me in Bu); 21.86
(d, PCH2, 1JP,C = 136.9 Hz); 22.33 (s, CH2Me in C8H17); 26.61
(s, CH2); 27.18 (s, CH2); 28.97 (s, CH2); 29.21 (s, CH2); 31.52
procedure.22 B.p. 175—176 С/42 Pa, nD 1.4520. 31P NMR
20
(CDCl3), : 25.5. 1H NMR, (: 0.96 (t, 6 H, Me, 3JH,H = 7.35 Hz);
1.22—1.74 (m, 12 H + 8 H, CH2); 2.55—2.64 (t, 4 H, NCH2);
2.90 (d, PCH2, 2JP,H = 10.26 Hz); 4.04—4.14 (dq, 4 H, ОCH2).
IR (thin layer), /cm–1: 1024 (Р=О).
3
(s, CH2); 32.25 (d, POCH2CH2, JP,C = 6.2 Hz); 46.22
This work was financially supported by the program of
the President of the Russian Federation "For Young PhD
Scientists" (Grant MKꢀ425.2010.3) and the Russian Founꢀ
dation for Basic Research (Project No. 10ꢀ03ꢀ00580а).
(s, CH2N); 53.05 (s, NCH2 in C8H17); 64.92 (s, OCH2); 64.98
(s, OCH2). IR (thin layer), /cm–1: 805, 852, 900, 965, 1024
(P—O—C), 1065, 1119, 1242 (ш, Р=О), 1308, 1380, 1438, 1466,
2864, 2925, 2957. Found (%): C, 67.84; H, 12.27; P, 6.55.
C26H56NO3P. Calculated (%): C, 67.64; H, 12.23; P, 6.71.
[2ꢀ(Dioctylamino)ethyl]diphenylphosphine oxide (5). Reacꢀ
tion conditions: 18 h at 100 С. The yield was 90% (after lyoꢀ
philic drying), viscous light yellow oil. 31Р NMR (CDCl3), :
31.57. 1Н NMR (CDCl3), : 0.84 (t, 6 H, Me, 3JH,H = 6.8 Hz);
1.20 (br.s, 16 H, CH2); 1.21—1.31 (m, 8 H, CH2); 2.32 (t, 4 H,
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3
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NMR (CDCl3), : 0.91 (t, 3 H, Me in C6H13, JH,H = 6.9 Hz);
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1
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Received June 29, 2011;
in revised form November 24, 2011