The synthesis and extraction properties of new 2-(phosphorylalkyl)-and 2-(phosphorylalkenyl)-substituted 1,8- and 1,6-naphthyridines

Article abstract of DOI:10.1007/s10593-016-1936-1

[Figure not available: see fulltext.] New 1,8- and 1,6-naphthyridines containing a phosphoryl group in the side chain were synthesized via Friedl?nder reaction by combining the appropriate aminonicotinic aldehydes and phosphoryl ketones in alcohol medium in the presence of basic catalysts (pyrrolidine or KOH). A series of phosphoryl-substituted 1,8-naphthyridines effectively extracted uranium(VI) from neutral aqueous solutions containing lanthanide(III) into 1,2-dichloroethane.

Full text of DOI:10.1007/s10593-016-1936-1

DOI 10.1007/s10593-016-1936-1
Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
The synthesis and extraction properties of new 2-(phosphorylalkyl)-
and 2-(phosphorylalkenyl)-substituted 1,8- and 1,6-naphthyridines
Georgy V. Bodrin1, Anna G. Matveeva1*, Evgenii I. Goryunov1, Margarita P. Pasechnik1,
Rinat R. Aysin1, Alexander N. Turanov2, Vasilii K. Karandashev3, Evgeny D. Savin1,
Alexander S. Peregudov1, Yulia V. Nelyubina1, Valery K. Brel1
1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 Vavilova St., Moscow 119991, Russia; e-mail: phoc@ineos.ac.ru
2 Institute of Solid State Physics, Russian Academy of Sciences,
2 Academician Ossipyan St., Chernogolovka 142432, Moscow District, Russia; e-mail: turanov@issp.ac.ru
3 Institute of Microelectronics Technology Problems and High Purity Materials, Russian Academy of Sciences,
6 Academician Ossipyan St., Chernogolovka 142432, Moscow District, Russia; e-mail: karan@iptm.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2016, 52(8), 583–591
Submitted June 21, 2016
Accepted July 27, 2016
New 1,8- and 1,6-naphthyridines containing a phosphoryl group in the side chain were synthesized via Friedlӓnder reaction by combin-
ing the appropriate aminonicotinic aldehydes and phosphoryl ketones in alcohol medium in the presence of basic catalysts (pyrrolidine or
KOH). A series of phosphoryl-substituted 1,8-naphthyridines effectively extracted uranium(VI) from neutral aqueous solutions contain-
ing lanthanide(III) into 1,2-dichloroethane.
Keywords: phosphoryl-substituted 1,8(1,6)-naphthyridines, extraction, f-elements, Friedlӓnder reaction.
Derivatives of 1,8- and 1,6-naphthyridines, synthesized
over the recent decades, have attracted the attention of
researchers by many potential applications in
biomedicine,1,2 catalysis,3 design of luminescent
chemosensors and markers.4 Recently it was also found
that 2-phosphoryl-substituted 1,8-naphthyridines can be
successfully used for the extraction of lanthanides from
carbonate-containing media.5 We have previously
demonstrated that 2-(phosphorylalkyl)-substituted 1,8- and
1,6-naphthyridines can be successfully obtained from
phosphoryl ketones in a Friedlӓnder reaction.6–8
A Friedlӓnder reaction between the appropriate nicotinic
aldehydes and phosphoryl ketones was used in this work
for the synthesis of a range of new 1,8- and 1,6-naphthy-
ridine derivatives containing a phosphoryl moiety in the
side chain. The obtained compounds 1b,c,e,f, 2a,b, 3, 4
(Fig. 1) were used for studying the extraction of uranium
(VI) and lanthanides(III) from neutral aqueous solutions.
The relationship between the ligand structure and the
extraction ability was identified. The extractive properties
of previously described naphthyridines 1a, 2c were also
studied for more accurate estimation of the effect of
structure on extraction parameters.
The phosphorylated naphthyridines 1b–f, 2b were
synthesized by refluxing phosphoryl ketones 5b–f with a
slight excess of aminonicotinic aldehydes 6, 7 in ethanol under
argon atmosphere in the presence of pyrrolidine (1.20 equiv)
and H2SO4 (0.05 equiv) as a regioselective catalyst6–9
R
N
R
R1
Ph
N
N
P
N
P
R1
Ph
O
O
1a R = H, R1 = Ph
b R = R1 = Ph
2a R = H
b R = Ph
c R = n-C5H11
c R = 2-thienyl, R1 = Ph
d R = 2-furyl, R1 = Ph
e R = n-C5H11, R1 = Ph
f R = Ph, R1 = i-Pr
N
Ph
Ph
N
N
P
N
P
Ph
Ph
O
O
3
4
Figure 1. Derivatives of 1,8- and 1,6-naphthyridines containing a
phosphoryl group in the side chain.
0009-3122/16/52(8)-0583©2016 Springer Science+Business Media New York
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Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
Scheme 1
The composition and structure of the obtained
compounds were confirmed by elemental analysis, data of
vibrational spectroscopy and multinuclear NMR spectro-
scopy, as well as X-ray structural analysis in the case of
compound 8.
IR spectra of the substituted 1,8-naphthyridines 1b–f
featured strong absorption bands at 1605–1609 and 1499–
1503 cm–1, and a medium intensity absorption band at
~1550 cm–1, which were characteristic for 1,8-naphthy-
ridine nucleus and belonged to the mixed vibrations of
ν(С–С)+ν(С–N)+δ(C–H).14–16 A strong line in the Raman
spectra at ~1370 cm–1 (mixed vibration of ν(С–С)+δ(С–Н))
and absorption bands at ~780 and ~540 cm–1 (interpreted as
"breathing" vibrations of the naphthyridine system (with
participation of both nitrogen atoms) coupled with δ(СН)
also were in good agreement with the structure of 1,8-
naphthyridine system.16 The main differences in vibrational
frequencies of 1,6- and 1,8-naphthyridines were due to the
lower degree of symmetry in the molecules of 1,6-
naphthyridines.14,15
The spectra of naphthyridines 2a–c exhibited the main
spectral characteristics of 1,6-naphthyridines: a strong IR
absorption band at 1613 cm–1 matched by a weak Raman
line, a strong Raman line at ~1590 cm–1 matched by a weaker
IR absorption band, as well as an IR absorption band at
~1550 cm–1 and Raman lines at ~1370 and ~540 cm–1.
For naphthyridines 3, 4 containing a double bond in the
linker, the ν(С=С) vibrations were likely mixed with the
similar ring vibration frequencies. Thus, the spectra in the
range of 1700–1600 cm–1 were somewhat different from
the spectra of naphthyridines 1b–f, 2a,b, and the band at
~1610 cm–1 can be assigned to a vibration containing
contribution of ν(С=С).
(Scheme 1). Despite the fact that the Friedlӓnder reaction
with unsymmetrical ketones may lead to the formation of a
mixture of 2- and 2,3-substituted naphthyridines,10,11 the
reaction of aldehydes 6, 7 with phosphoryl ketones 5b–f
under these conditions produced only a single regioisomer
(Scheme 1).
Only the reaction of phosphoryl ketone 5a with
aldehyde 7 gave a mixture of isomeric naphthyridines 2a
and 8 in 70 and 30% yields, respectively, according to 31Р
NMR data (Scheme 2). The individual compounds 2a and
8 could be isolated by fractional crystallization of this
mixture in 11 and 2% yields, respectively.
Scheme 2
Identification of vibrations due to the thiophene and
furan substituents in compounds 1c,d was impossible,
because the series of absorption bands of these rings were
close to the vibration frequencies of the naphthyridine
system, while the ν(С–S) absorption band in the region of
~700 cm–1 overlapped with the intense absorption bands due
to the deformation vibrations of phenyl rings. The ν(Р=О)
vibrations were observed at a frequency typical for
diphenylphosphoryl group, at 1185–1175 cm–1 in all the
studied naphthyridines except compound 8, which differed
from the other studied naphthyridines by having a short
linker (the spectrum of compound 8 contained absorption
bands at 1186 and 1168 cm–1). Compound 1f contained
isopropyl substituents instead of phenyl groups at the
phosphorus atom, and thus had a lower vibration frequency,
with the ν(Р=О) absorption at 1145 cm–1.
The preparation of naphthyridines 3 and 4 by using
pyrrolidine as catalyst was complicated due to side reactions
that were likely caused by the addition of this amine at the
double bond of the starting phosphoryl enone 9.12 For this
reason, KOH was used as catalyst13 (Scheme 3), although it
caused partial resinification of the reaction mixture and
decreased the product yields.
Scheme 3
1Н and 13С–{1H} NMR signals were interpreted based
on a set of 2D NMR experiments (1Н–1Н COSY, HMQC,
and HMBC). The CH2 group within the –CH2CHR– linker
connecting the naphthyridine system with the phosphoryl
group in compounds 1b–e, 2b was next to an asymmetric
carbon atom, therefore its signal was a part of АВMX
system in 1Н NMR spectra, where М and Х were
respectively the Н and Р nuclei of CHP(O)Ph2 fragment, or
1
АВМ system in Н–{31P} NMR spectra. The reason for this
effect was the prochiral nature of СН2 group, according to the
584

Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
concept described by Hanson.17 The hydrogen atoms in this
moiety were diastereotopic and, thus, anisochronic (i.e.,
characterized by different chemical shifts) in achiral
medium. It should be noted that the molecules of
naphthyridines 1b–e, 2b contained another prochiral center,
the phosphorus atom, thus the phenyl substituents bonded
to this center must also be diastereotopic. This was mani-
fested both in 1Н, 1Н–{31P} spectra, as well as in 13С–{1H}
spectra, which featured doubled 13C NMR signals of the
aromatic rings linked to phosphorus (the ortho, meta, para,
and ipso atoms).
In the case of naphthyridine 1f, the prochiral centers
were not only the phosphorus atom and methylene carbon
atom in the –СН2СНPh– linker, but also both α-carbon
atoms of the isopropyl groups. Therefore, isopropyl groups
themselves and СН3 substituents at each of these groups
will be diastereotopic. This created conditions for the
manifestation of so-called double magnetic non-
Figure 2. The molecular structure of compound 8 with atoms
represented by thermal vibration ellipsoids of 50% probability.
in the extraction of U(VI) and Eu(III) ions, first of all the
substantial difference between the isomeric 1,8- and 1,6-
naphthyridines should be noted when comparing the pairs
of compounds 1a–2a, 1b–2b, 1e–2с (Table 1). The DM
values in these pairs differed by several times. Obviously,
the main reason for different extraction ability between the
isomers 1–2 was the difference in their coordinating ability.
Thus, it is known that the phosphorylated 1,8-naphthy-
ridines showed tridentate ONN-coordination in complexes
with lanthanide salts.22 The coordinating properties of
phosphoryl-substituted 1,6-naphthyridines have not been
studied, however, it can be expected from their structure
that complex formation with lanthanides will occur either
by monodentate interaction with the cation via P=O→M
bond, or by O,N-bidentate coordination. Obviously, the
stability of complexes is higher in the case of tridentate
interaction, compared to mono– and bidentate coordination,
and thus the extraction efficiency with 1,8-naphthyridines
will be higher than with the isomeric 1,6-naphthyridines.
The complex formation between phosphoryl-substituted
1,8- and 1,6-naphthyridines and uranyl cations has not yet
been investigated. However, the efficiency of uranium(VI)
extraction by some 1,8-naphthyridines (ligands 1a,e,f,
Table 1) is so high that participation of both ring nitrogen
atoms in coordination with uranyl cation/cations is assumed.
It should be noted that the extraction efficiency was
much lower and nearly identical in the case of specially
1
equivalence in the respective NMR spectra.18 Indeed, Н
NMR spectrum of compound 1f in CDCl3 solution
contained two multiplets (double septets) of the methine
protons in isopropyl groups and four double doublets
belonging to the methyl group protons. These multiplets in
1Н–{31P} NMR spectrum of naphthyridine 1f were
transformed into two septets and four doublets,
respectively. The double magnetic nonequivalence effect
was similarly observed also in 13С–{1H} NMR spectrum of
compound 1f, which showed two doublets belonging to
anisochronic α-carbon atoms of isopropyl fragments and
four doublets of carbon atoms in the magnetically non-
equivalent methyl groups of these substituents. Thus,
naphthyridine 1f belongs to a rare type of structures where
a system of prochiral centers giving rise to double magnetic
nonequivalence in NMR spectra contains not only the usual
carbon atoms,18–20 but also a tetracoordinated pentavalent
phosphorus atom.*
The structure of naphthyridine 8 was additionally
confirmed by X-ray structural analysis (Fig. 2). According
to the obtained data, the geometry parameters for compound
8 were quite close to those of the previously described
2-[(1-diphenylphosphoryl-1-methyl)ethyl]-1,6-naphthyridine
(10).8 In both cases we should note the cissoid
configuration of the P=O group relative to the naphthyri-
dine moiety. The pseudotorsion angle OPC(14)C(15) in the
structure of naphthyridine 8 was equal to 5.9°, while in the
structure of the analogous compound 10 it was 3.0°.8
The properties of naphthyridines 1a–f, 2a–с, 3, 4 with
regard to the extraction of f-elements were studied by using
the extraction of uranium(VI) and lanthanides(III) from
neutral aqueous solutions into 1,2-dichloroethane as an
example. Since the values of distribution ratios found for
lanthanides had no significant differences, only the data for
europium and uranium are discussed further (Table 1).
When considering the correlation between the structure
of phosphoryl-substituted naphthyridine and its efficiency
synthesized model isomers
3
and 4, where the
naphthyridine moiety and the phosphoryl group were
linked by a –CH=CH– fragment (Table 1). According to
Table 1. Extraction properties of 2-phosphoryl-substituted 1,8- and
1,6-naphthyridines 1a–f, 2a–с, 3, 4
Distribution ratios*
Distribution ratios
Compound
Compound
DEu
DU
DEu
DU
3.9
< 0.1
< 0.1
8.9
125
5.8
1.5
186
436
< 0.1
< 0.1
< 0.1
< 0.1
< 0.1
48
0.21
2.6
1.5
0.76
1a
1b
1c
1e
1f
2a
2b
2с
3
*The phenomenon of double magnetic nonequivalence in NMR spectra of
systems containing a prochiral phosphorus atom was first reported by
M. I. Kabachnik with coworkers.21
1.8
4
* DM = [Morg]/[Maq], where М – metal.
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Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
conformational analysis data, the presence of a double
bond in the linker prevented simultaneous coordination of
the oxygen atom of phosphoryl group and nitrogen atom/
atoms of the naphthyridine moiety to one metal cation. It
should be also pointed out that the DM values for ligands 3
and 4 (Table 1) were close to the DM value of phosphine
oxide (p-Tol)2P(O)CH2Ph determined under the same
experimental conditions: DEu < 0.1 and DU = 7.24.
The introduction of substituent R at the α-position of
–CH2CHR– linker had a substantial effect on the extraction
efficiency. The substituent altered not only the lipophilic
properties of extragent, but also the stability of extracted
complexes by changing the basicity of phosphoryl group,
and thus also the strength of the P=O→M coordination
bond. The inductive effect of p-C5H11 substituent increased
the phosphoryl group basicity (as well as ligand
lipophilicity), while the introduction of a phenyl or thienyl*
substituent decreased the basicity of the Р=О group (when
comparing the DM values in the series of ligands 1a–c,e and
2а–c).
The replacement of phenyl substituents at the phosphorus
atom with more electron-donating isopropyl substituents
(ligands 1b,f) increased the basicity of Р=О group, thus
improving the stability of the extracted complexes and
raising the DU and DEu values of extractant 1f (Table 1).
The obtained results showed that the 2-phosphoryl-
substituted 1,8-naphthyridines 1a,e,f were effective and
selective extractants for the recovery of uranium and can be
used for the extraction of trace amounts of uranium from
aqueous solutions of lanthanides.
Thus, we have used the Friedlӓnder reaction to
synthesize a range of new 2-phosphorylethyl-substituted
1,8- and 1,6-naphthyridines from the respective nicotinic
aldehydes and phosphoryl-substituted ketones. The
composition and molecular structure of the products were
established from elemental analysis, vibrational (IR,
Raman) spectroscopy and multinuclear (1H, 31P, 13C) NMR
spectroscopy. Several of the obtained 1,8-naphthyridines
effectively extracted uranium from neutral aqueous
solutions into 1,2-dichloroethane. The extraction efficiency
depended on the nature of substituents at the phosphorus
atom, as well as the substituent at the α-position of the
ethylene linker between the naphthyridine system and the
phosphoryl group.
the compounds were acquired on a Bruker Avance 600
1
spectrometer (600 and 125 MHz, respectively). Н–{31P}
and 31Р–{1H} NMR spectra were acquired on a Bruker
Avance 400 spectrometer (400 and 162 MHz,
respectively). The solvent was CDCl3, the concentration of
solutions was 0.025 mol/l (compound 8) or 0.1 mol/l (the
rest of the compounds). Residual solvent signals were used
1
as internal standard in Н and 13С NMR spectra (7.26 ppm
1
for Н nuclei, 77.0 ppm for 13С nuclei), 85% H3PO4 was
used as external standard in 31P NMR spectra. Elemental
analysis was performed at the Laboratory of Microanalysis,
Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences; the content of C, H, and N
was determined on a Carlo Erba 1106 instrument, the content
of P and S was determined according to published proce-
dures.23 Melting points were determined in open capillaries
on a Stanford Research Systems MPA120 EZ-melt
automated melting point apparatus and were not corrected.
Ethanol was of anhydrous grade, purchased from Scharlau,
pyrrolidine was purchased from Acros Organics, H2SO4
was of chemically pure grade (98% assay). All other
solvents were purified by standard procedures prior to use.
The reaction progress was controlled by 31Р NMR spectra
of the reaction mixtures. Phosphoryl ketones 5a–f and 9
were synthesized according to literature,8,24 nicotinic
aldehydes 6, 7 – according to another published procedure.25
Synthesis of 2-phosphoryl-substituted 1,8- and 1,6-
naphthyridines 1b–f, 2a,b, 8 (General method).6–8
A
mixture of phosphoryl ketone 5a–f (2.50 mmol) and
aminonicotinic aldehyde 6 or 7 (2.63 mmol, 1.05 equiv)
was treated with EtOH (10 ml) and 2 ml of ethanol solution
containing pyrrolidine (0.26 g, 3.00 mmol, 1.20 equiv) and
H2SO4 (13 mg, 0.13 mmol, 0.05 equiv). The obtained
mixture was stirred and refluxed for 7–12 h. The precipitate
that formed in the reaction mixture was separated, washed,
and recrystallized. If precipitate was absent after the
reaction completion, ethanol was removed at reduced
pressure (12 mmHg), the residue was dissolved in CHCl3
(20 ml), the solution was washed with water (3×20 ml),
dried over anhydrous Na2SO4, evaporated to dryness at
reduced pressure, and recrystallized. The obtained product
was dried at reduced pressure (120–140°С, 12 mmHg) for
2–4 h.
Naphthyridines 1a7, 2c,8 and the phosphine oxide
(p-Tol)2P(O)CH2Ph26 were synthesized and purified
according to the respective procedures. Compound 2c was
characterized by vibrational spectra that were not
previously reported.8
Experimental
IR spectra in the range of 400–4000 cm–1 were recorded
on a Bruker Tensor 37 FTIR spectrometer in KBr pellets.
Raman spectra in the range of 100–3500 cm–1 were
recorded on a Jobin-Yvon LabRAM 300 spectrometer,
equipped with a microscope and laser ССD detector. The
He–Ne laser emission line with 632.8 nm was used for
excitation at a power not higher than 2 mW. 1Н and 13С–{1H}
NMR spectra of compounds 1d, 2b, 8 were acquired on a
Bruker Avance 400 spectrometer (400 and 100 MHz,
respectively). 1Н and 13С–{1H} NMR spectra for the rest of
2-[(2-Diphenylphosphoryl-2-phenyl)ethyl]-1,8-naphthy-
ridine (1b) was obtained from phosphoryl ketone 5b
(0.70 g, 2.01 mmol) and aldehyde 6 (0.26 g, 2.13 mmol).
The reaction time was 9 h. Yield 0.70 g (81%), white fine
crystalline powder, mp 254–256°С (CHCl3–EtOAc, 1:3).
IR spectrum, ν, cm–1: 1608, 1560, 1548, 1499, 1453, 1437
(Ph), 1185, 1174 (Р=О), 1119, 1102, 1072, 847, 811, 753,
716, 697, 549, 534. Raman spectrum, ν, cm–1: 1604, 1593,
1372, 1193, 1048, 1038, 1029, 1000 (Ph), 811, 779, 755,
1
692, 617, 536. H NMR spectrum, δ, ppm (J, Hz): 3.72
* Compound 1d with a furyl substituent was not studied due to its low
stability.
(1Н, ddd, 2J = 14.6, 3J = 4.4, 3JHP = 8.3) and 3.78 (1Н, ddd,
586

Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
3
3
4
2J = 14.6, J = 10.6, JHP = 8.5, CH2CH); 4.75 (1Н, ddd,
3J = 3.9, J = 1.7, H-7). 13С–{1H} NMR spectrum, δ, ppm
3
2
1
3J = 5.0, J = 10.4, JHP = 5.4, CH2СН); 7.01 (1H, t,
(J, Hz): 39.8 (CH2CH); 41.0 (d, JCP = 69.7, CH2CH);
3J = 6.9, H-4 CPh); 7.05 (2H, t, 3J = 7.3, H-3,5 CPh); 7.06
121.3 (C-4a); 121.6 (C-6); 123.8 (C-3); 124.8 (d,
3
3
4
4
(1H, d, J = 8.7, H-3); 7.22 (2H, td, J = 7.5, JHP = 2.3,
4JCP = 2.8, C-5'); 126.5 (d, JCP = 2.8, C-4'); 127.7 (d,
3
H-3,5 PPh); 7.31 (1H, t, J = 7.5, H-4 PPh); 7.36 (2H, d,
3JCP = 6.6, C-3'); 128.1 (d, 3JCP = 11.6, C-3,5 Ph); 128.8 (d,
3J = 7.3, H-2,6 CPh); 7.41 (1H, dd, 3J = 7.9, 3J = 4.2, H-6);
3JCP = 11.6, C-3,5 Ph); 131.0 (d, JCP = 8.8, C-2,6 Ph);
2
7.44–7.52 (5H, m, H PPh); 7.82 (1H, d, 3J = 8.2, H-4); 8.04
131.3 (d, 1JCP = 95.1, C-1 Ph); 131.5 (d, 4JCP = 3.9, C-4 Ph);
131.5 (d, 2JCP = 8.3, C-2,6 Ph); 131.7 (d, 1JCP = 100.6, C-1 Ph);
3
4
(1H, dd, J = 7.9, J = 1.3, H-5); 8.06–8.13 (2H, m, H-2,6
PPh); 9.08 (1H, dd, 3J = 3.9, 4J = 1.6, H-7). 1H–{31P} NMR
spectrum, δ, ppm (J, Hz): 3.73 (1Н, dd, 2J = 14.6, 3J = 5.1)
4
131.8 (d, JCP = 2.8, C-4 Ph); 136.9 (C-4); 137.0 (C-5);
137.3 (d, 2JCP = 6.1, C-2'); 153.3 (br. s, C-7); 155.7 (C-8a);
2
3
3
and 3.78 (1Н, dd, J = 14.7, J = 10.7, СН2CH); 4.75 (1Н,
163.1 (d, JCP = 13.3, C-2). 31P–{1H} NMR spectrum, δ,
3
3
3
dd, J = 4.8, J = 10.1, CH2СН); 7.01 (1H, t, J = 6.9, H-4
ppm: 32.6. Found, %: C 70.97; H 4.83; N 6.35; P 7.12;
S 7.34. C26H21N2OPS. Calculated, %: C 70.89; H 4.81;
N 6.36; P 7.03; S 7.28.
3
CPh); 7.05 (2H, t, J = 7.7, H-3,5 CPh); 7.06 (1H, d,
3J = 8.3, H-3); 7.22 (2H, t, J = 7.5, H-3,5 PPh); 7.31 (1H,
3
t, 3J = 7.5, H-4 PPh); 7.36 (2H, d, 3J = 7.0, H-2,6 CPh); 7.41
(1H, dd, 3J = 8.0, 3J = 4.3, H-6); 7.44–7.52 (5H, m, H PPh);
7.82 (1H, d, 3J = 8.2, H-4); 8.05 (1H, dd, 3J = 8.0, 4J = 1.1,
H-5); 8.06–8.13 (2H, m, H-2,6 PPh); 9.09 (1H, dd, 3J = 3.8,
4J = 1.4, H-7). 13С–{1H} NMR spectrum, δ, ppm (J, Hz):
38.8 (CH2CH); 45.6 (d, 1JCP = 67.4, CH2CH); 121.2 (C-4a);
2-{[2-Diphenylphosphoryl-2-(furan-2-yl)]ethyl}-1,8-
naphthyridine (1d) was obtained from phosphoryl ketone
5d (1.01 g, 2.98 mmol) and aldehyde 6 (0.37 g, 3.03 mmol)
The reaction time was 8 h. Yield 0.66 g (52%), white
crystalline powder, mp 215–216°С (CHCl3–hexane, 1:5).
IR spectrum, ν, cm–1: 1607, 1549, 1503, 1436 (Ph), 1178
(P=O), 1148, 1122, 1101, 856, 812, 750, 728, 699, 549,
526. Raman spectrum, ν, cm–1: 1609, 1594, 1551, 1496,
1374, 1002 (Ph), 822, 797, 783, 732, 690, 645, 618, 537.
1H NMR spectrum, δ, ppm (J, Hz): 3.65 (1Н, ddd,
2J = 14.6, 3J = 4.4, 3JHP = 7.8) and 3.78 (1Н, ddd, 2J = 14.6,
5
121.6 (C-6); 123.8 (C-3); 126.8 (d, JCP = 2.2, C-4 CPh);
3
4
128.0 (d, JCP = 12.2, C-3,5 PPh); 128.1 (d, JCP = 1.1,
3
C-3,5 CPh); 128.7 (d, JCP = 11.1, C-3,5 PPh); 130.1 (d,
3JCP = 5.5, C-2,6 CPh); 130.9 (d, JCP = 8.8, C-2,6 PPh);
2
4
2
131.2 (d, JCP = 2.8, C-4 PPh); 131.5 (d, JCP = 8.3,
4
3
3
C-2,6 PPh); 131.6 (d, JCP = 2.2, C-4 PPh); 131.7 (d,
3J = 11.0, JHP = 7.7, CH2CH); 4.96 (1Н, ddd, J = 4.4,
1JCP = 94.5, C-1 PPh); 132.1 (d, 1JCP = 99.5, C-1 PPh); 135.7
3J = 11.0, JHP = 8.3, CH2CH); 6.04–6.07 (2H, m, H-3',4');
2
2
(d, JCP = 5.0, C-1 CPh); 136.8 (C-4); 136.9 (C-5); 153.3
7.10–7.12 (1H, m, H-5'); 7.20 (1H, d, 3J = 8.3, H-3); 7.31–
(C-7); 155.7 (C-8a); 163.4 (d, JCP = 13.3, C-2). 31P–{1H}
7.37 (2H, m, H-3,5 Ph); 7.39–7.49 (5H, m, H-6, H-3,4,5,4' Ph);
3
3
NMR spectrum, δ, ppm: 33.5. Found, %: C 76.97; H 5.34;
N 6.61; P 7.26. C28H23N2OP. Calculated, %: C 77.41;
H 5.34; N 6.45; P 7.13.
7.58–7.65 (2H, m, H-2,6 Ph); 7.92 (1H, d, J = 8.3, H-4);
3
7.96–8.03 (2H, m, H-2,6 Ph); 8.07 (1H, dd, J = 8.1,
4J = 1.9, H-5); 9.06 (1H, dd, J = 4.3, J = 1.9, H-7).
3
4
2-{[2-Diphenylphosphoryl-2-(thiophen-2-yl)]ethyl}-
1,8-naphthyridine (1c) was obtained from phosphoryl
ketone 5c (0.88 g, 2.48 mmol) and aldehyde 6 (0.31 g,
2.53 mmol). The reaction time was 7 h. Yield 0.60 g
(55%), white fine crystalline powder, mp 251–253°С
(2-PrOH). IR spectrum, ν, cm–1: 1607, 1550, 1503, 1436
(Ph), 1249, 1174 (Р=О), 1145, 1121, 1093, 853, 796, 727,
715, 696, 594, 564, 529. Raman spectrum, ν, cm–1: 1595,
1H–{31P} NMR spectrum, δ, ppm (J, Hz): 3.66 (1Н, dd,
2J = 14.6, J = 4.0) and 3.77 (1Н, dd, J = 14.6, J = 11.0,
3
2
3
CH2CH); 4.96 (1Н, dd, 3J = 4.4, J = 10.9, CH2CH); 6.04–
3
6.08 (2H, m, H-3',4'); 7.10–7.12 (1H, m, H-5'); 7.20 (1H, d,
3J = 8.2, H-3); 7.34 (2H, t, J = 7.4, H-3,5 Ph); 7.38–7.49
3
(5H, m, H-6, H-3,4,5,4' Ph); 7.59–7.64 (2H, m, H-2,6 Ph);
3
7.91 (1H, d, J = 8.3, H-4); 7.96–8.02 (2H, m, H-2,6 Ph);
3
4
8.07 (1H, dd, J = 8.1, J = 1.7, H-5); 9.06 (1H, dd,
1
4
1431, 1375, 1001 (Ph), 840, 783, 731, 669, 618, 537. H
3J = 4.2, J = 2.0, H-7). 13С–{1H} NMR spectrum, δ, ppm
2
1
NMR spectrum, δ, ppm (J, Hz): 3.66 (1Н, ddd, J = 14.5,
(J, Hz): 36.6 (CH2CH); 40.2 (d, JCP = 69.0, CH2CH);
3J = 4.8, 3JHP = 7.4) and 3.69 (1Н, ddd, 2J = 14.5, 3J = 10.3,
109.4 (d, 3JCP = 5.9, C-3'); 110.4 (d, 4JCP = 2.2, C-4'); 121.3
3JHP = 7.4, СН2CH); 5.10 (1Н, ddd, J = 4.8, J = 10.7,
2JHP = 6.3, СН2CH); 6.68 (1H, dd, 3J = 3.8, 3J = 4.9, H-4');
6.92–6.95 (2H, m, H-3',5'); 7.12 (1H, d, 3J = 8.3, H-3); 7.28
(C-4a); 121.6 (C-6); 123.4 (C-3); 128.1 (d, JCP = 12.5,
3
3
3
C-3,5 Ph); 128.7 (d, 3JCP = 11.7, C-3,5 Ph); 131.1 (d, 2JCP = 9.5,
C-2,6 Ph); 131.3 (d, 1JCP = 95.4, C-1 Ph); 131.5 (d, 2JCP = 8.8,
C-2,6 Ph); 131.6 (d, 4JCP = 2.9, C-4 Ph); 131.6 (d, 1JCP = 100.5,
3
4
(2H, dt, J = 7.7, JHP = 3.0, H-3,5 Ph); 7.34–7.38 (1H, m,
H-4 Ph); 7.41 (1H, dd, 3J = 8.0, 3J = 4.4, H-6); 7.43–7.48 (3H,
m, H 3,4,5 Ph); 7.57–7.63 (2H, m, H-2,6 Ph); 7.86 (1H, d,
3J = 8.2, H-4); 8.04–8.09 (3H, m, H-5, H-2,6 Ph); 9.08 (1H,
4
C-1 Ph); 131.8 (d, JCP = 2.2, C-4 Ph); 136.9 (C-5); 137.0
4
2
(C-4); 141.9 (d, JCP = 2.9, C-5'); 149.0 (d, JCP = 7.3,
3
C-2'); 153.3 (C-7); 155.7 (C-8a); 163.2 (d, JCP = 13.2,
dd, J = 4.2, J = 2.0, H-7). H–{31P} NMR spectrum, δ,
C-2). 31P–{1H} NMR spectrum, δ, ppm: 31.8. Found, %:
C 73.50; H 4.94; N 6.61; P 7.39. C26H21N2O2P. Calculated,
%: C 73.57; H 4.99; N 6.60; P 7.30.
3
4
1
2
3
ppm (J, Hz): 3.67 (1Н, dd, J = 14.2, J = 5.0) and 3.70
2
3
(1Н, dd, J = 14.4, J = 9.8, СН2CH); 5.11 (1Н, dd,
3J = 5.6, 3J = 9.7, СН2CH); 6.66–6.71 (1H, m, H-4'); 6.92–
6.97 (2H, m, H-3',5'); 7.13 (1H, d, 3J = 8.2, H-3); 7.29 (2H,
2-[(2-Diphenylphosphoryl)hept-1-yl]-1,8-naphthyridine
(1e) was obtained from phosphoryl ketone 5e (0.68 g,
1.96 mmol) and aldehyde 6 (0.26 g, 2.13 mmol). The reaction
time was 8 h. Yield 0.58 g (63%), white fine crystalline
powder, mp 194–195°С (EtOAc–cyclohexane, 1:4).
IR spectrum, ν, cm–1: 1609, 1549, 1500, 1454, 1438 (Ph),
3
3
t, J = 7.4, H-3,5 Ph); 7.36 (1H, t, J = 7.3, H-4 Ph); 7.42
(1H, dd, 3J = 8.0, 3J = 4.2, H-6); 7.44–7.49 (3H, m, H-3,4,5
Ph); 7.61 (2H, d, 3J = 7.5, H-2,6 Ph); 7.87 (1H, d, 3J = 8.2,
H-4); 8.03–8.10 (3H, m, H-5, H-2,6 Ph); 9.08 (1H, dd,
587

Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
1371, 1307, 1263, 1179 (Р=О), 1118, 1102, 1073, 854, 794,
d, 3J = 7.3) and 1.47 (3H, d, 3J = 7.3, CH(СН3)2); 1.85 (1H,
3 3
780, 758, 714, 700, 566, 543. Raman spectrum, ν, cm–1:
1610, 1594, 1576, 1550, 1374, 1045, 1031, 1000 (Ph), 782,
693, 617, 536. 1H NMR spectrum, δ, ppm (J, Hz): 0.64 (3H,
sept, J = 7.3, CHMe2); 2.40 (1H, sept, J = 7.4, CHMe2);
2 3
3.68 (1H, dd, J = 14.2, J = 11.6) and 3.79 (1H, dd,
3
3
2J = 14.2, J = 3.5, CH2CH); 4.12 (1H, dd, J = 11.6,
3
3
t, J = 6.8, CH3); 0.92–1.08 (4H, m, CH2CH2CH3); 1.10–1.36
3J = 3.4, CH2CH); 6.93 (1H, d, J = 8.2, H-3); 7.10 (1H, tm,
3
(2H, m, CH2(CH2)2CH3); 1.55–1.77 (2H, m, CH2(CH2)3CH3);
3J = 7.2, H-4 Ph); 7.15 (1H, tm, J = 7.2, H-3,5 Ph); 7.38–
2
3
3
3.31 (1H, ddd, J = 15.3, J = 8.2, JHP = 12.8) and 3.43
7.44 (3H, m, H-6, H-2,6 Ph); 7.83 (1H, d, 3J = 8.2, H-4); 8.06
2
3
3
3
4
3
(1H, ddd, J = 15.3, J = 5.4, JHP = 12.0, CH2CH); 3.67–
(1H, dd, J = 8.1, J = 2.0, H-5); 9.07 (1H, dd, J = 3.8,
4J = 1.2, H-7). 13С–{1H} NMR spectrum, δ, ppm (J, Hz):
16.0 (d, 2JCP = 2.2, CH3); 16.5 (d, 2JCP = 1.7, CH3); 17.2 (d,
2JCP = 2.8, CH3); 17.7 (d, 2JCP = 2.2, CH3); 26.6 (d, 1JCP = 63.0,
3.73 (1H, m, CH2CH); 7.15–7.20 (2H, m, H-3,5 Ph); 7.22
3
(1H, d, J = 8.3, H-3); 7.20–7.24 (1H, m, H-4 Ph); 7.44
(1H, dd, 3J = 8.0, 3J = 4.4, H-6); 7.42–7.49 (3H, m, H-3,4,5
3
1
Ph); 7.79–7.84 (2H, m, H-2,6 Ph); 7.90 (1H, d, J = 8.0,
CHMe2); 26.7 (d, JCP = 59.7, CHMe2); 39.8 (CH2CH);
3
1
H-4); 7.86–7.91 (2H, m, H-2,6 Ph); 8.10 (1H, dd, J = 8.0,
41.8 (d, JCP = 55.8, CH2CH); 121.1 (C-4a); 121.5 (C-6);
4J = 1.8, H-5); 9.10 (1H, dd, 3J = 4.2, 4J = 2.0, H-7). 1H–{31P}
NMR spectrum, δ, ppm (J, Hz): 0.65 (3H, t, 3J = 6.7, CH3);
0.92–1.10 (4H, m, CH2CH2CH3); 1.10–1.40 (2H, m,
CH2(CH2)2CH3); 1.54–1.79 (2H, m, CH2(CH2)3CH3); 3.31
123.6 (C-3); 126.9 (d, JCP = 1.7, C-4 Ph); 128.4 (br. s,
5
C-3,5 Ph); 129.8 (d, 3JCP = 5.0, C-2,6 Ph); 136.6 (C-4); 137.0
2
(C-5); 137.2 (d, JC3P = 5.0, C-1 Ph); 153.3 (C-7); 155.8
(C-8a); 163.8 (d, JCP = 12.7, C-2). 31P–{1H} NMR
spectrum, δ, ppm: 56.5. Found, %: C 72.19; H 7.49;
N 7.64; P 8.49. C22H27N2OP. Calculated, %: C 72.11;
H 7.43; N 7.64; P 8.45.
2
3
2
(1H, dd, J = 15.3, J = 8.2) and 3.43 (1H, dd, J = 15.3,
3J = 5.4, CH2CH); 3.66–3.74 (1H, m, CH2CH); 7.15–7.20
3
(2H, m, H-3,5 Ph); 7.22 (1H, d, J = 8.5, H-3); 7.20–7.25
3
3
(1H, m, H-4 Ph); 7.44 (1H, dd, J = 7.8, J = 4.2, H-6);
2-[(2-Diphenylphosphoryl)ethyl]-1,6-naphthyridine (2a)
was obtained from phosphoryl ketone 5a (2.15 g, 7.90 mmol)
and aldehyde 7 (1.03 g, 8.43 mmol). The reaction time was
8 h. The product was isolated by repeated recrystallization
from a mixture of compounds 2a and 8. Yield 0.31 g
(11%), white fine crystalline powder, mp 173–174°С
(EtOAc). IR spectrum, ν, cm–1: 1613, 1591, 1557, 1483,
1467, 1437 (Ph), 1401, 1229, 1179 (Р=О), 1119, 1108,
969, 944, 854, 775, 755, 726, 695, 546. Raman spectrum,
ν, cm–1: 1610, 1590, 1571, 1559, 1468, 1373, 1352, 1341,
7.43–7.50 (3H, m, H-3,4,5 Ph); 7.80–7.84 (2H, m, H-2,6
3
Ph); 7.87–7.91 (2H, m, H-2,6 Ph); 7.90 (1H, d, J = 8.4,
3
4
H-4); 8.10 (1H, dd, J = 8.1, J = 1.9, H-5); 9.10 (1H, dd,
3J = 4.2, J = 1.9, H-7). 13С–{1H} NMR spectrum, δ, ppm
4
3
(J, Hz): 13.8 (CH3); 22.1 (CH2CH3); 27.2 (d, JCP = 8.9,
CH2(CH2)2CH3); 28.2 (CH2(CH2)3CH3); 31.7 (CH2CH2CH3);
36.0 (d, 1JCP = 70.8, CH2CH); 36.8 (CH2CH); 121.2 (C-4a);
3
121.5 (C-6); 123.7 (C-3); 128.2 (d, JCP = 11.1, C-3,5 Ph);
128.5 (d, 3JCP = 11.0, C-3,5 Ph); 130.9 (d, 2JCP = 8.8, C-2,6 Ph);
4
2
1
131.0 (d, JCP = 2.2, C-4 Ph); 131.0 (d, JCP = 8.8, C-2,6 Ph);
1156, 1026, 995 (Ph), 789, 684, 675, 614, 536. H NMR
131.4 (d, 4JCP = 2.2, C-4 Ph); 132.7 (d, 1JCP = 94.0, C-1 Ph); 132.9
spectrum, δ, ppm (J, Hz): 2.91–2.99 (2H, m, CH2CH2P);
1
3
(d, JCP = 94.9, C-1 Ph); 136.8 (C-5); 136.9 (C-4); 153.3
3.33–3.40 (2H, m, CH2CH2P); 7.38 (1H, d, J = 8.5, H-3);
(C-7); 155.7 (C-8a); 164.3 (d, JCP = 9.9, C-2). 31P–{1H}
7.43–7.47 (4H, m, H-3,5 Ph); 7.48–7.52 (2H, m, H-4 Ph);
3
3
NMR spectrum, δ, ppm: 36.4. Found, %: C 75.54; H 6.77;
N 6.56; P 7.24. C27H29N2OP. Calculated, %: C 75.68; H 6.82;
N 6.54; P 7.23.
7.77–7.83 (5H, m, H-8, H-2,6 Ph); 8.12 (1H, d, J = 8.5,
H-4); 8.72 (1H, d, 3J = 5.9, H-7); 9.19 (1H, br. s, H 5). 1H–{31P}
NMR spectrum, δ, ppm (J, Hz): 2.91–3.00 (2H, m,
CH2CH2P); 3.32–3.42 (2H, m, CH2CH2P); 7.38 (1H, d,
3J = 8.4, H-3); 7.42–7.47 (4H, m, H-3,5 Ph); 7.48–7.53
(2H, m, H-4 Ph); 7.77–7.84 (5H, m, H-8, H-2,6 Ph); 8.12
2-[(2-Diisopropylphosphoryl-2-phenyl)ethyl]-1,8-naphthy-
ridine (1f) was obtained from phosphoryl ketone 5f (0.56 g,
2.00 mmol) and aldehyde 6 (0.26 g, 2.13 mmol). The
reaction time was 9 h. Yield 0.55 g (75%), white fine
crystalline powder, mp 205–206°С (CHCl3–hexane, 1:4).
IR spectrum, ν, cm–1: 1605, 1548, 1501, 1454, 1145 (Р=О),
887, 857, 816, 780, 748, 702, 634, 542. Raman spectrum,
ν, cm–1: 1604, 1584, 1550, 1454, 1372, 1038, 1004 (Ph),
3
(1H, d, J = 8.4, H-4); 8.72 (1H, d, 3J = 5.9, H-7); 9.19 (1H,
br. s, H-5). 13С–{1H} NMR spectrum, δ, ppm (J, Hz): 28.3 (d,
2
1JCP = 71.9, CH2CH2P); 30.8 (d, JCP = 1.1, CH2CH2P);
121.7 (C-8); 122.5 (C-4a); 123.2 (C-3); 128.7 (d,
3JCP = 11.6, C-3,5 Ph); 130.8 (d, 2JCP = 9.4, C-2,6 Ph); 131.8
(d, 4JCP = 2.2, C-4 Ph); 132.7 (d, 1JCP = 99.5, C-1 Ph); 135.8
(C-4); 147.0 (C-7); 150.1 (C-8a); 152.4 (C-5); 165.6 (d,
3JCP = 13.8, C-2). 31P–{1H} NMR spectrum, δ, ppm: 32.0.
Found, %: C 74.01; H 5.14; N 7.76; P 8.57. C22H19N2OP.
Calculated, %: C 73.73; H 5.34; N 7.82; P 8.64.
1
783, 751, 537. H NMR spectrum, δ, ppm (J, Hz): 0.88
3
3
3
(3H, dd, J = 7.3, JHP = 15.1) and 1.44 (3H, dd, J = 7.4,
3JHP = 14.8, CH(СН3)2); 1.10 (3H, dd, J = 7.3, JHP = 14.5)
3
3
3
3
and 1.47 (3H, dd, J = 7.2, JHP = 14.5, CH(СН3)2); 1.85
(1H, d sept, 3J = 7.4, 2JHP = 14.8, CHMe2); 2.39 (1H, d sept,
2
2
3J = 7.2, JHP = 14.4, CHMe2); 3.68 (1H, ddd, J = 14.2,
2-[(2-Diphenylphosphoryl-2-phenyl)ethyl]-1,6-naphthy-
ridine (2b) was obtained from phosphoryl ketone 5b (0.87 g,
2.50 mmol) and aldehyde 7 (0.31 g, 2.53 mmol). The
reaction time was 12 h. Yield 0.82 g (76%), white fine
crystalline powder, mp 183–184°С (MeCN, followed by
EtOAc). IR spectrum, ν, cm–1: 1613, 1592, 1557, 1483,
1438 (Ph), 1400, 1175 (Р=О), 1120, 1102, 1071, 845, 754,
724, 716, 697, 593, 549. Raman spectrum, ν, cm–1: 1605,
1593, 1559, 1376, 1193, 1001 (Ph), 791, 692, 617, 542.
3J = 11.7, 3JHP = 5.3) and 3.79 (1H, ddd, 2J = 14.3, 3J = 3.4,
3JHP = 5.8, CH2CH); 4.12 (1H, ddd, J = 11.5, J = 3.6,
3
3
2JHP = 5.3, CH2CH); 6.93 (1H, d, J = 8.2, H-3); 7.10 (1H,
3
t, 3J = 6.9, H-4 Ph); 7.15 (1H, t, 3J = 7.4, H-3,5 Ph); 7.39–7.43
(3H, m, H-6, H-2,6 Ph); 7.83 (1H, d, 3J = 8.2, H-4); 8.06 (1H,
dd, J = 8.0, 4J = 1.8, H-5); 9.07 (1H, dd, J = 4.1, J = 1.9,
3
3
4
H-7). H–{31P} NMR spectrum, δ, ppm (J, Hz): 0.88 (3H,
1
d, 3J = 7.4) and 1.44 (3H, d, 3J = 7.4, CH(СН3)2); 1.10 (3H,
588

Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
3
3
1H NMR spectrum, δ, ppm (J, Hz): 3.72 (1H, ddd, 2J = 15.0,
(1H, d, J = 16.8, CH=CHP); 8.20 (1H, dd, J = 8.1,
3J = 5.8, 3JHP = 8.9) and 3.74 (1H, ddd, J = 14.9, J = 8.8,
4J = 1.7, H-5); 8.24 (1H, d, J = 8.2, H-4); 9.13 (1H, dd,
2
3
3
3
3
4
3JHP = 8.8, CH2CH); 4.55 (1H, ddd, J = 6.0, J = 8.9,
2JHP = 6.7, CH2CH); 7.02–7.11 (3H, m, H-3,4,5 CPh); 7.09
(1H, d, 3J = 8.4, H-3); 7.21–7.27 (2H, m, H-3,5 PPh); 7.29–
7.36 (3H, m, H-2,6 CPh, H-4 PPh); 7.43–7.54 (5H, m,
H PPh); 7.83 (1H, d, 3J = 5.9, H-8); 7.91 (1H, dd, 3J = 8.4,
4J = 0.6, H-4); 7.99–8.07 (2H, m, H-2,6 PPh); 8.70 (1H, d,
3J = 5.9, H-7); 9.09 (1H, br. s, H-5). 1H–{31P} NMR spectrum,
3J = 4.1, J = 1.9, H-7). 13С–{1H} NMR spectrum, δ, ppm
(J, Hz): 122.5 (C-6); 122.9 (C-4a); 123.0 (C-3); 128.2 (d,
1JCP = 99.5, CH=CHP); 128.7 (d, JCP = 12.2, C-3,5 Ph);
3
131.4 (d, 2JCP = 9.9, C-2,6 Ph); 132.1 (d, JCP = 2.2, C-4 Ph);
4
1
132.5 (d, JCP = 105.0, C-1 Ph); 136.9 (C-5); 138.4 (C-4);
145.2 (d, 2JCP = 3.3, CH=CHP); 154.5 (C-7); 155.8 (C-8a);
160.0 (d, JCP = 17.7, C-2). 31P–{1H} NMR spectrum, δ,
3
2
3
δ, ppm (J, Hz): 3.72 (1H, dd, J = 15.1, J = 5.8) and 3.74
ppm: 23.8. Found, %: C 74.11; H 4.80; N 7.65; P 8.64.
C22H17N2OP. Calculated, %: C 74.15; H 4.81; N 7.86; P 8.69.
trans-2-[(2-Diphenylphosphoryl)vinyl]-1,6-naphthy-
ridine (4) was obtained analogously to compound 3 from
aldehyde 7 (0.22 g, 1.80 mmol) and phosphoryl ketone 9
(0.46 g, 1.70 mmol). After heating for 3 h, the solvent was
removed by evaporation at reduced pressure and the solid
residue was treated as described in the procedure for
preparation of compound 3. Yield 0.24 g (40%), white fine
crystalline powder, mp 204–206°С (EtOAc). IR spectrum,
ν, cm–1: 1611, 1587, 1550, 1483, 1438 (Ph), 1400, 1234,
1196, 1183 (Р=О), 1160, 1120, 1099, 1071, 1001, 829,
785, 755, 739, 721, 693, 561, 547, 530, 523, 513. Raman
spectrum, ν, cm–1: 1620, 1610 (C=C), 1591, 1574, 1554,
1371, 1332, 1184, 1161, 1029, 1002 (Ph), 790, 693, 617, 540.
1H NMR spectrum, δ, ppm (J, Hz): 7.49–7.54 (4H, m, H-3,5
2
3
(1H, dd, J = 14.9, J = 8.9, CH2CH); 4.55 (1H, dd,
3J = 6.0, 3J = 8.7, CH2CH); 7.02–7.07 (1H, m, H-4 CPh); 7.08
(2H, t, 3J = 7.3, H-3,5 CPh); 7.09 (1H, d, 3J = 8.4, H-3); 7.24
(2H, t, 3J = 7.5, H-3,5 PPh); 7.29–7.36 (3H, m, H-4 PPh, H-2,6
3
CPh); 7.43–7.53 (5H, m, H PPh); 7.83 (1H, d, J = 5.9,
3
H-8); 7.91 (1H, d, J = 8.4, H-4); 8.00–8.07 (2H, m, H-2,6
3
PPh); 8.70 (1H, d, J = 5.9, H-7); 9.09 (1H, br. s, H-5).
13С–{1H} NMR spectrum, δ, ppm (J, Hz): 39.1 (CH2CH);
1
45.6 (d, JCP = 67.5, CH2CH); 121.7 (C-8); 122.3 (C-4a);
5
123.9 (C-3); 127.0 (d, JCP = 2.2, C-4 CPh); 128.0 (d,
3JCP = 11.7, C-3,5 PPh); 128.2 (d, JCP = 2.2, C-3,5 CPh);
4
3
3
128.7 (d, JCP = 11.7, C-3,5 PPh); 129.9 (d, JCP = 5.1,
2
C-2,6 CPh); 131.0 (d, JCP = 8.8, C-2,6 PPh); 131.3 (d,
4JCP = 2.2, C-4 PPh); 131.4 (d, 2JCP = 8.8, C-2,6 PPh); 131.7
1
4
(d, JCP = 94.6, C-1 PPh); 131.7 (d, JCP = 2.2, C-4 PPh);
1
3
132.0 (d, JCP = 100.5, C-1 PPh); 135.3 (C-4); 135.6 (d,
Ph); 7.55–7.59 (2H, m, H-4 Ph); 7.68 (1H, d, J = 8.5,
2JCP = 5.1, C-1 CPh); 146.8 (C-7); 150.1 (C-8a); 152.4 (C-5);
H-3); 7.76 (1H, dd, 3J = 17.0, 3JHP = 18.6, CH=CHP); 7.80
3
3
3
164.5 (d, JCP = 12.5, C-2). 31P–{1H} NMR spectrum, δ,
(1H, dd, J = 17.0, JHP = 22.9, CH=CHP); 7.79–7.84 (4H,
3
ppm: 33.2. Found, %: C 77.27; H 5.24; N 6.31; P 7.09.
C28H23N2OP. Calculated, %: C 77.41; H 5.34; N 6.45;
P 7.13.
2-[(2-Diphenylphosphoryl)hept-1-yl]-1,6-naphthyridine
(2c). IR spectrum, ν, cm–1: 1613, 1591, 1558, 1483, 1467,
1437 (Ph), 1403, 1374, 1339, 1311, 1232, 1179 (Р=О),
1116, 844, 715, 700, 636, 568, 551, 542. Raman spectrum, ν,
cm–1: 1614, 1594, 1559, 1469, 1375, 1340, 1030, 1000
(Ph), 791, 676, 618, 542.
m, H-2,6 Ph); 7.88 (1H, d, J = 5.9, H-8); 8.33 (1H, d,
3J = 8.5, H-4); 8.76 (1H, d, 3J = 5.9, H-7); 9.28 (1H, br. s, H-5).
1H–{31P} NMR spectrum, δ, ppm (J, Hz): 7.51 (4H, t,
3J = 7.3, H-3,5 Ph); 7.55–7.60 (2H, m, H-4 Ph); 7.68 (1H,
3
3
d, J = 8.4, H-3); 7.76 (1H, d, J = 17.0, CH=CHP); 7.81
(1H, d, 3J = 16.7, CH=CHP); 7.80–7.84 (4H, m, H-2,6 Ph);
7.89 (1H, d, 3J = 6.0, H-8); 8.33 (1H, d, 3J = 8.5, H-4); 8.77
3
(1H, d, J = 6.0, H-7); 9.28 (1H, br. s, H-5). 13С–{1H}
NMR spectrum, δ, ppm (J, Hz): 122.1 (C-8); 122.8 (C-3);
3
trans-2-[(2-Diphenylphosphoryl)vinyl]-1,8-naphthy-
ridine (3). A solution of aldehyde 6 (0.36 g, 2.94 mmol)
and phosphoryl ketone 9 (0.74 g, 2.74 mmol) in EtOH
(5 ml) was treated with KOH (8 mg, 0.14 mmol) as 20%
aqueous solution. The mixture was refluxed for 3 h. The
precipitate that formed upon cooling was recrystallized
from EtOH and dried for 2 h at reduced pressure (120°С,
12 mmHg). Yield 0.43 g (44%), white crystalline powder,
mp 269–270°С (EtOH). IR spectrum, ν, cm–1: 1610, 1596,
1547, 1501, 1437 (Ph), 1185 (Р=О), 1119, 1103, 994, 838,
822, 807, 778, 750, 743, 722, 693, 580, 549, 524, 517.
Raman spectrum, ν, cm–1: 1608 (C=C), 1592, 1376, 1274,
123.3 (C-4a); 128.8 (d, JCP = 12.2, C-3,5 Ph); 128.9 (d,
1JCP = 98.4, CH=CHP); 131.5 (d, JCP = 9.9, C-2,6 Ph);
2
1
4
132.2 (d, JCP = 107.3, C-1 Ph); 132.2 (d, JCP = 2.2, C-4
2
Ph); 136.9 (C-4); 145.5 (d, JCP = 3.3, CH=CHP); 147.4
3
(C-7); 150.4 (C-8a); 152.8 (C-5); 157.1 (d, JCP = 17.7,
C-2). 31P–{1H} NMR spectrum, δ, ppm: 23.8. Found, %:
C 74.05; H 4.74; N 7.77; P 8.55. C22H17N2OP. Calculated,
%: C 74.15; H 4.81; N 7.86; P 8.69.
3-[(Diphenylphosphoryl)methyl]-2-methyl-1,6-naphthy-
ridine (8) was obtained after the isolation of compound 2a
from the reaction mixture. The residue obtained after
evaporation of the combined filtrates was repeatedly
recrystallized. Yield 50 mg (2%), white crystalline solid,
mp 199–200°С (EtOAc–hexane). IR spectrum, ν, cm–1:
1617, 1586, 1559, 1479, 1439, 1401, 1234, 1212, 1186,
1168, 1135, 1121, 1108, 1093, 1070, 944, 915, 831, 819,
742, 719, 691, 577, 543, 517, 506, 478, 460. Raman
spectrum, ν, cm–1: 1616, 1590, 1575, 1558, 1400, 1371,
1
998 (Ph), 776, 691, 614, 533. H NMR spectrum, δ, ppm
(J, Hz): 7.44–7.50 (5H, m, H-6, H-3,5 Ph); 7.51–7.55 (2H,
3
m, H-4 Ph); 7.62 (1H, d, J = 8.3, H-3); 7.76–7.82 (4H, m,
3
3
H-2,6 Ph); 7.82 (1H, dd, J = 16.9, JHP = 18.3, CH=CHP);
3
2
8.01 (1H, dd, J = 16.7, JHP = 24.7, CH=CHP); 8.19 (1H,
dd, J = 8.1, 4J = 2.0, H-5); 8.24 (1H, d, 3J = 8.2, H-4); 9.13
3
1
(1H, dd, 3J = 4.1, 4J = 2.1, H-7). 1H–{31P} NMR spectrum, δ,
ppm (J, Hz): 7.44–7.51 (5H, m, H-6, H-3,5 Ph); 7.51–7.57
1361, 1025, 996 (Ph), 741, 682, 663, 615, 438. H NMR
spectrum, δ, ppm (J, Hz): 2.65 (3H, s, CH3); 3.86 (2H, d,
2JHP = 13.5, CH2); 7.47–7.54 (4H, m, H-3,5 Ph); 7.57–7.63
(2H, m, H-4 Ph); 7.69–7.76 (4H, m, H-2,6 Ph); 7.79 (1H, d,
3
(2H, m, H-4 Ph); 7.63 (1H, d, J = 8.3, H-3); 7.77–7.82
(4H, m, H-2,6 Ph); 7.82 (1H, d, 3J = 17.4, CH=CHP); 8.01
589

Chemistry of Heterocyclic Compounds 2016, 52(8), 583–591
4
3J = 6.0, H-8); 7.88 (1H, d, JHP = 2.8, H-4); 8.68 (1H, d,
References
3J = 5.9, H-7); 9.02 (1H, br. s, H-5). H–{31P} NMR
1
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spectrum, δ, ppm (J, Hz): 2.65 (3H, s, CH3); 3.86 (2H, s,
CH2); 7.50 (4H, t, 3J = 7.5, H-3,5 Ph); 7.60 (2H, t, 3J = 7.4,
3
H-4 Ph); 7.73 (4H, d, J = 7.2, H-2,6 Ph); 7.79 (1H, d,
3J = 5.9, H-8); 7.88 (1H, s, H-4); 8.68 (1H, d, 3J = 5.9, H-7);
9.02 (1H, br. s, H-5). 13С–{1H} NMR spectrum, δ, ppm (J, Hz):
24.4 (CH3); 34.8 (d, 1JCP = 64.9, CH2); 121.2 (C-8); 122.4 (d,
4JCP = 1.6, C-4a); 125.9 (d, JCP = 8.0, C-3); 128.9 (d,
2
3JCP = 11.2, C-3,5 Ph); 131.1 (d, 2JCP = 9.6, C-2,6 Ph); 131.7
(d, 1JCP = 101.7, C-1 Ph); 132.4 (d, 4JCP = 2.4, C-4 Ph); 136.7
(d, 3JCP = 4.8, C-4); 146.8 (C-7); 148.9 (d, 5JCP = 1.6, C-8a);
152.1 (C-5); 164.0 (d, 3JCP = 4.0, C-2). 31P–{1H} NMR spect-
rum, δ, ppm: 28.9. Found, %: C 73.81; H 5.34; N 7.77; P 8.61.
C22H19N2OP. Calculated, %: C 73.73; H 5.34; N 7.82; P 8.64.
X-ray structural analysis of compound 8. Crystals of
compound 8 (M 358.38) suitable for X-ray structural
analysis were obtained by isothermal evaporation of its
solution in EtOAc–hexane mixture. X-ray structural
analysis was performed on a Bruker SMART APEX II
CCD diffractometer (MoKα-radiation, graphite mono-
chromator, ω-scanning). The structure was solved by direct
method and refined by method of least squares in
anisotropic full matrix approximation by F2hkl. The
hydrogen atom positions were calculated geometrically and
refined in isotropic approximation by the "rider" model. All
calculations were performed with the SHELXTL PLUS
software suite.27 The complete X-ray structural dataset for
compound 8 has been deposited at the Cambridge
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Investigation
of
the
extraction
properties.
1,2-Dichloroethane of chemically pure grade was used
without additional purification as the organic solvent.
Solutions of extractants at 0.01 mol/l concentration were
prepared from accurately weighed samples. The initial
aqueous U(VI) and lanthanide(III) solutions were prepared
by dissolving the respective perchlorates in water, followed
by the addition of NH4ClO4. The initial concentrations of
metal ions were 4·10–6 mol/l, the concentration of NH4ClO4
was 1 mol/l. The phases were contacted at room tempe-
rature by agitation with a stirrer at 60 rpm for 1 h, which is
sufficient for establishing constant values of distribution
ratios. The concentration of lanthanides(III) and U(VI)
in the initial and equilibrated aqueous solutions was
determined by mass spectrometry with inductively coupled
plasma ionization of samples (ICP-MS), using a Thermo
Elemental X-7 mass spectrometer according to a published
method.28 The content of elements in the organic phase was
determined after reextraction with a 0.1 М solution of
hydroxyethylidenediphosphonic acid. The distribution
ratios for the elements were calculated as ratios of the
equilibrium concentration in the organic and aqueous
phases (DM = [Morg]/[Maq]). The error of the determined DM
values did not exceed 5%.
This work was performed with financial support from
the Russian Foundation for Basic Research (grant No.
14-03-00695-а).
590

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591