Synthesis, structure, and complexing ability of fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-dicarbonyl) compounds

Article abstract of DOI:10.1134/S107042800712007X

New fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono) bis(1,3-diketones) and 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(3- oxopropionates) were synthesized by azo coupling of the corresponding 1,3-dicarbonyl compounds with biphenyl-4,4′-bis(diazoni

Full text of DOI:10.1134/S107042800712007X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 12, pp. 1781–1787. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © I.V. Shchur, O.G. Khudina, Ya.V. Burgart, V.I. Saloutin, M.A. Grishina, V.A. Potemkin, 2007, published in Zhurnal Organicheskoi
Khimii, 2007, Vol. 43, No. 12, pp. 1780–1786.
Synthesis, Structure, and Complexing Ability of Fluoroalkyl-
Containing 2,2′-(Biphenyl-4,4′-diyldihydrazono)bis(1,3-
dicarbonyl) Compounds
I. V. Shchura, O. G. Khudinaa, Ya. V. Burgarta, V. I. Saloutina,
M. A. Grishinab, and V. A. Potemkinb
a Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences,
ul. S. Kovalevskoi 20, Yekaterinburg, 620219 Russia
e-mail: saloutin@ios.uran.ru
b Chelyabinsk State University, Chelyabinsk, Russia
Received February 7, 2007
Abstract—New fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketones) and 2,2′-(bi-
phenyl-4,4′-diyldihydrazono)bis(3-oxopropionates) were synthesized by azo coupling of the corresponding
1,3-dicarbonyl compounds with biphenyl-4,4′-bis(diazonium) dichloride. Complexing ability of the obtained
bis-hydrazones was studied, and new coordination compounds of the general formula M2L2 [where M = Ni(II),
Cu(II); L = fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketone)] were obtained.
DOI: 10.1134/S107042800712007X
enol and azo–hydrazone tautomerism (Scheme 2). In
addition, isomerism related to different orientation of
substituents with respect to the C=N bond is possible
(e.g., isomers A and B in Scheme 2).
In the recent years, strong interest in transition
metal chelates has arisen due to prospects in their ap-
plication for the preparation of polyfunctional mag-
netoactive materials [1]. We previously [2] synthesized
fluoroalkyl-substituted 2-arylhydrazono-1,3-dicarbonyl
compounds which were converted into fluorinated
ligands via reactions with nucleophiles. While con-
tinuing studies in this line, we examined reactions of
fluorinated 1,3-diketones Ia–If and 3-oxoalkanoates
IIa–IId with biphenyl-4,4′-bis(diazonium) dichloride
in aqueous alcohol in the presence of sodium acetate
(Scheme 1). Compounds IIIa–IIIf and IVa–IVd thus
obtained may exist as three symmetric isomers A, C,
and D and three asymmetric isomers E–G due to keto–
1
The H and 19F NMR spectral patterns of com-
pounds IIIa–IIIf and IVa–IVd in CDCl3 cannot be
interpreted unambiguously. Hydrazones IIIb, IIIc, and
IIIe having a bulky benzoyl group and even bulkier
pivaloyl substituent in CDCl3 solution exist as two
isomers, as follows from the presence of double sets of
1
19
signals in their H and F NMR spectra. Compounds
IIIa, IIId, IIIf, and IVa–IVd with smaller acyl and
alkoxycarbonyl groups displayed in the NMR spectra
only one set of signals (see Experimental).
Scheme 1.
RF
3
O
R
2
o
m
NaOAc
EtOH–H2O
H
·
·
N
H···O
N
·
O
O
p
1
i
Cl– N2
N2 Cl–
+
N
N
R
O
O···H
RF
R
RF
Ia–If, IIa–IId
IIIa–IIIf, IVa–IVd
I, III, R = Me (a, f), Ph (b, e), t-Bu (c), Bu (d); RF = CF3 (a–c), HCF2CF2 (b, d), C3F7 (e), C4F9 (f); II, IV, R = EtO (a, c),
MeO (b, d); RF = CF3 (a), HCF2CF2 (b), C3F7 (c), C4F9 (d).
1781

SHCHUR et al.
1782
RF
···
O
R
H
N
RF
RF
O
R
RF
O
N
O
H
O
R
H
N
N
N
N
O
N
N
O···H
R
O
A
B
C
D
RF
RF
O
R
O
R
N
RF
N
RF
N
N
O
O
N
N
O
O
O···H
N
H
O···H
N
H
R
R
E
F
R
O
·
·
·
H
N
RF
O
N
N
O
O
RF
N
H
R
G
The absence of a signal assignable to CH=N proton
in the H NMR spectra of these compounds rules out
parameters to determine the structure of new isomeric
bis-hydrazones IIIa–IIIc and IVa (RF = CF3, R = Me,
Ph, t-Bu, OEt). Compounds IIIa (R = Me) and IVa
(R = OEt) in CDCl3 were thus assigned structure A
1
symmetric and asymmetric tautomers D, F, and G.
Moreover, the NMR spectra lacked two sets of signals
with equal intensities; therefore, asymmetric structures
E–G should be excluded. The IR spectra of solutions
of IIIc–IIIf and IVa in chloroform and crystalline
samples of the same compounds contained two strong
absorption bands in the region 1670–1725 cm–1. This
may be due to the presence of two nonequivalent
carbonyl groups in their molecules, as in symmetric
bis-hydrazone structures A and B. The low-frequency
shift of the carbonyl bands, as compared to the data
given in [3], results from conjugation with the C=N
bond and aromatic fragments, as well as from intra-
molecular hydrogen bonding with participation of the
carbonyl oxygen atom. Thus it remained to distinguish
between isomers A and B with different orientations of
substituents at the double C=N bond.
1
2
4
(δF ~91–92 ppm, JCF = 292.7, JCF = 32.7, JCF
=
1 Hz), while bis-hydrazone IIIb having bulky benzoyl
groups was found to exist in CDCl3 and DMF-d7 as
a mixture of isomers A (δF 93.92 ppm in DMF-d7) and
B (δF 87.87 ppm in DMF-d7), the former strongly
prevailing (A:B ≈ 10:1). The presence of a tert-butyl
group, which creates considerable steric hindrances to
intramolecular hydrogen bonding with participation of
the neighboring carbonyl group in IIIc, favors in-
1
creased fraction of isomer A (A: δF 92.03 ppm, JCF
=
2
1
292.6, JCF = 32.1 Hz; B: δF 89.19 ppm, JCF = 288,
2JCF = 37.1 Hz; A:B ≈ 6:5; CDCl3).
Compound IIIe possessing heptafluoroacyl and
benzoyl substituents exists in CDCl3 as a mixture of
two isomers. As we showed previously [4], the forma-
tion of intramolecular hydrogen bond between the
CF3CO carbonyl oxygen atom and proton of the aryl-
hydrazone fragment in CF3-containing hydrazones and
bis-hydrazones induces a diamagnetic shift of the CF3
fluorine nuclei in the 19F NMR spectra. Comparison of
the chemical shifts of fluorine nuclei in the α-CF2
group (neighboring to the carbonyl group) of two
isomers of IIIe indicated prevalence of isomer A in
19
13
We previously [4] defined some F and C NMR
parameters typical of isomers A and B of trifluoro-
methyl-containing 1,2,3-trione 2-arylhydrazones. These
1
2
are δF ~91–92 ppm, JCF ≈ 292, and JCF ≈ 31–34 Hz
for the free CF3C=O group (isomer A, CDCl3) and
1
2
δF ~87–88 ppm, JCF ≈ 287, and JCF ≈ 40 Hz for the
CF3C=O group involved in intramolecular hydrogen
bond (isomer B, CDCl3). We tried to use the above
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007

SYNTHESIS, STRUCTURE, AND COMPLEXING ABILITY
1783
We can conclude that isomeric composition of com-
pounds IIIa–IIIf and IVa–IVd is determined mainly
by steric factor. If steric hindrances are absent (com-
pounds IIIa, IIId, IIIf, and IVa–IVd), the bis-hydra-
zones in CDCl-3 exist exclusively as isomers A; bis-
hydrazones IIIb, IIIc, and IIIe having bulky substit-
uents (such as phenyl or tert-butyl group) give rise to
mixtures of isomers A and B.
chloroform-d (A: 91%, δα-F 49.27 ppm; B: 9%,
δα-F 48.06 ppm; cf. the data given above for CF3-
containing bis-hydrazone IIIb).
On the other hand, the X-ray diffraction data
showed that bis-hydrazone IIIe in crystal exists only as
isomer A (see figure). Presumably, crystallization of
IIIe from a solution in CHCl3 is accompanied by com-
plete transformation of isomer B into sterically more
favorable isomer A. The X-ray diffraction data unam-
biguously indicated formation of intramolecular hydro-
gen bond between the NH protons of the arylhydra-
zone fragments and benzoyl carbonyl oxygen atoms.
The distances O1 ···H2 and O1′···H2′ are 1.97(2) and
1.92(4) Å, and the bond angles N2H2O1 and C1O1H2
are 131(1) and 104(9)°, respectively [∠N2′H2′O1′
134(1)°, ∠C1′O1′H2′ 99(4)°]. Molecule IIIe is charac-
terized by trans orientation of the triketone hydrazone
fragments with respect to the biphenyl moiety.
Using the MOPS algorithm [5] we have searched
for most favorable isomers of trifluoromethyl-con-
taining hydrazones IIIa–IIIc and ester IVa, and the
energy, charge, and orbital parameters of the isomers
found have been calculated ab initio using 6-31G basis
set (see table). It is seen that isomers A of compounds
IIIa–IIIc and IVa are more stable than the correspond-
ing isomers B, which is consistent with the experi-
mental data for solutions in CDCl3 and DMF-d7 and
crystalline state, obtained by NMR and IR spectros-
copy and X-ray analysis. The energy difference be-
tween isomers A and B ranges from 33 to 50 kJ/mol.
For all these compounds, the oxygen atom involved in
intramolecular hydrogen bonding in isomer A have
a smaller charge (qO) than the corresponding oxygen
atom in isomer B. For example, qO = –0.635 and
–0.634 in A and qO = –0.569 and –0.568 in B (IIIa).
Charges on the NH hydrogen atoms in both isomers
are approximately equal. Thus the calculation results
showed that the formation of isomer A is more favor-
able from the energy viewpoint and that it is more
stable than B due to formation of a stronger intra-
molecular hydrogen bond.
Likewise, diethyl 2,2′-(biphenyl-4,4′-diyldihydra-
zono)bis(4,4,5,5,6,6,6-heptafluoro-3-oxopropionate)
(IVc) and bis-hydrazones IIIf and IVd having nona-
fluorobutyl substituents at the carbonyl groups are
likely to have structure A (CDCl3). The chemical shifts
of the α-CF2 fluorine nuclei (δα-F 49.43–50.25 ppm) are
comparable with that found for the predominant
isomer of IIIe (A: δF 49.27 ppm); a paramagnetic shift
is observed relative to the corresponding signal of
isomer B of IIIe (δα-F 48.06 ppm). The chemical shifts
19
of the α-fluorine nuclei in the F NMR spectra of bis-
hydrazones IIId and IVb containing tetrafluoroethyl
groups (CDCl3; δF 42.28–42.59 ppm) are similar to
those reported for isomers A of tetrafluoroethyl-
substituted 1,2,3-trione 2-arylhydrazones (δF 42.05–
44.26 ppm) [4].
Using compound IIIe as an example, we showed
that newly synthesized bis-hydrazones III are capable
of forming complexes with metals. By treatment of
F5
F6
C9′
C5
F7
C8′
O1′
C7′
F4
C4
C3
F2
H2′
N2′
C10′
C18′
C1′
C2′
F3
N1
F1
C12′
O3′
C17′
C16′
C11′
C17
C13′
O3
C12
C18
C13
N1′
F3′
F1′
C6′
C16
C15
C3′
C4′
C14′
C2
C1
C15′
N2
H2
F4′
C7
C14
C11
C10
F2′
F5′
C5′
O1
C9
F6′
C8
F7′
Structure of the molecule of 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-dione) (IIIe)
according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007

SHCHUR et al.
1784
Calculated total energies, charges on the carbonyl carbon and oxygen atoms, and the corresponding frontier orbital Fukui
indices of isomers A and B of bis-hydrazones IIIa–IIIc and IVa
Charges on atoms (Fukui indices for HOMO/LUMO)
Comp. no.,
isomer
Etot, kJ/mol
C1=O
C1=O
C1′=O
C1′=O
C3=O
C3=O
C3′=O
C3′=O
IIIa, A
IIIa, B
IIIb, A
IIIb, B
IIIc, A
IIIc, B
IVa, A
IVa, B
–5153612.89
–5153579.41
–6157461.58
–6157411.77
–5770493.38
–5770452.00
–5753761.38
–5753718.95
0.5545
(0.0018/
0.03)00
–0.6354
(0.0064/
0.0274)
0.5527
(0.0021/
0.0322)
–0.6339
(0.0064/
0.0286)
0.3747
(0.0008/
0.0415)
–0.4603
(0.0078/
0.0393)
0.3723
(0.0009/
0.0444)
–0.4578
(0.0077/
0.0404)
0.5274
(0.0004/
0.0075)
–0.5305
(0.0062/
0.0049)
0.5271
(0.0005/
0.0091)
–0.5294
(0.0062/
0.0052)
0.3773
(0.003/
0.0765)
–0.5686
(0.0097/
0.0755)
0.3764
(0.0031/
0.0850)
–0.568
(0.0097/
0.0834)
0.5054
(0.0029/
0.055)0
–0.6181
(0.0051/
0.0448)
0.5054
(0.0029/
0.0551)
–0.6172
(0.0051/
0.0448)
0.3526
(0.0015/
0.0450)
–0.4563
(0.0067/
0.0307)
0.3525
(0.0015/
0.0456)
–0.4568
(0.0068/
0.0313)
0.4991
(0.0007/
0.0220)
–0.5255
(0.0056/
0.0083)
0.4991
(0.0007/
0.0219)
–0.5256
(0.0056/
0.0083)
0.3553
(0.0039/
0.0845)
–0.5530
(0.0087/
0.0816)
0.3553
(0.0039/
0.0841)
–0.5529
(0.0087/
0.0812)
0.6085
(0.0011/
0.0278)
–0.6497
(0.0057/
0.0285)
0.5812
(0.0034/
0.0314)
–0.6304
(0.0053/
0.0219)
0.3877
(0.0004/
0.0572)
–0.4807
(0.0080/
0.0595)
0.3781
(0.0014/
0.0368)
–0.4527
(0.0059/
0.0259)
0.5873
(0.0001/
0.0029)
–0.5404
(0.0057/
0.0025)
0.5577
(0.0006/
0.0152)
–0.5405
(0.0056/
0.0051)
0.3695
(0.003/
.0662)
–0.6009
(0.0102/
0.0627)
0.3604
(0.0041/
0.1047)
–0.5744
(0.0098/
0.0993)
0.9084
(0.0009/
0.0178)
–0.6527
(0.0039/
0.0173)
0.9102
(0.0012/
0.0206)
–0.651
(0.0038/
0.0183)
0.3728
(0.0002/
0.032)
–0.465
(0.0079/
0.0403)
0.3723
(0.0003/
0.0357)
–0.4631
(0.0079/
0.043)
0.8643
(0.0001/
0.0053)
–0.5594
(0.0048/
0.006)0
0.8754
(0.0002/
0.006)0
–0.5679
(0.0047/
0.0057)
0.3749
(0.0012/
0.0701)
–0.5429
(0.0077/
0.074)0
0.3785
(0.0012/
0.0683)
–0.5430
(0.0075/
0.0714)
The presence of molecular ion peaks in the mass
spectra confirmed binuclear nature of such chelates.
bis-hydrazone IIIe with nickel(II) or copper(II) acetate
we obtained coordination compounds VIa and VIb.
According to the elemental analysis data, complexes
VIa and VIb have a composition of 2:2 [M2L2, where
M = Ni(II) or Cu(II) and L = IIIe – 2H+] (Scheme 3).
Unfortunately, complexes VIa and VIb turned out to
decompose in ethanol, CHCl3, pyridine, and DMSO to
give the initial ligand; therefore, it was difficult to ex-
amine them by NMR spectroscopy and grow crystals
suitable for X-ray analysis. Taking into account that
the carbonyl oxygen atoms involved in intramolecular
hydrogen bonding (in benzoyl or pivaloyl groups)
possess smaller negative charges (see table), we
presumed that nonfluorinated carbonyl fragments also
participate in coordination with metals. Analogous
complexes derived from fluorine-free 2,2′-(biphenyl-
4,4′-diyldihydrazono)bis(cyclohexane-1,3-dione) and
3,3′-(biphenyl-4,4′-diyldihydrazono)bis(pentane-2,4-
dione) [6] were more stable, and they were studied by
UV spectroscopy (in alcohol) and mass spectrometry.
Thus we have synthesized new fluoroalkyl-contain-
ing ligands, 2,2′-(biphenyl-4,4′-diyldihydrazono)bis-
(1,3-ketones) and 2,2′-(biphenyl-4,4′-diyldihydrazono)-
bis(3-oxoalkanoates), and Ni(II) and Cu(II) chelates
derived therefrom. The new ligands are polyfunctional
compounds which may be used as synthons for design
of various open-chain and heterocyclic ligands.
EXPERIMENTAL
The melting points were determined using open
capillaries and were not corrected. The IR spectra
(400–4000 cm–1) were recorded on a Perkin–Elmer
Spectrum One spectrometer with Fourier transform
from samples dispersed in mineral oil (IIIa–IIIf, IVa–
IVd) and 0.1 M solutions in chloroform (IIIc, IIId,
1
IIIf, IVa). The H, 13C, and 19F NMR spectra were
measured on a Bruker DRX-400 spectrometer (400,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007

SYNTHESIS, STRUCTURE, AND COMPLEXING ABILITY
1785
Scheme 2.
C3F7
C3F7
O
O
C3F7
N
N
2M(OAc)2 (Va, Vb)
MeOH–H2O–DMF
MeCOONa, 80°C
O
Ph
N
N
N
Ph
· · ·
N
H
N
O
O
O
O
O
M
M
N
2 Ph
N
N
Ph
O
O···H
Ph
O
N
Ph
O
N
C3F7
C3F7
C3F7
IIIe
VIa, VIb
M = Ni (a), Cu (b).
100.6, and 376 MHz, respectively) using tetramethyl-
General procedure for the synthesis of bis-
hydrazones IIIa–IIIf and IVa–IVd. A solution of
514 mg (2 mmol) of biphenyl-4,4′-diamine in dilute
hydrochloric acid (prepared by diluting 6.7 ml of con-
centrated hydrochloric acid with 21 ml of water) was
cooled to 0°C, and a solution of 276 mg of sodium
nitrite in 1.2 ml of water was added under vigorous
stirring. Solutions of 1.82 g of sodium acetate in 16 ml
of water and of 4 mmol of 1,3-dicarbonyl compound
Ia–If or IIa–IId in 13 ml of ethanol were mixed
separately, and the above diazonium salt solution was
slowly added under stirring, maintaining the tempera-
ture at 10°C. The precipitate was filtered off, recrystal-
lized from ethanol (unless otherwise stated), and dried.
1
13
silane (internal; H, C) and C6F6 (19F) as reference.
The elemental compositions were determined on
a Perkin–Elmer PE 2400 Series II analyzer.
Quantum-chemical calculations (SCF MO LCAO,
ab initio 6-31G) of compounds IIIa–IIIc and IVa were
performed at the SKIF Cluster of the United State of
Russia and Byelorussia.
The X-ray diffraction study of a single crystal of
compound IIIe was performed at room temperature on
a KM-4 Kuma Diffraction diffractometer (MoKα irra-
diation, graphite monochromator, ω/2θ scanning, tem-
perature 100 2 K). The structure was solved by the
direct methods, followed by Fourier syntheses, using
SHELXS-97 software package [7] and was then
refined by the least-squares procedure in full-matrix
anisotropic approximation for all non-hydrogen atoms
(SHELXL-97) [7]. The coordinates of hydrogen atoms
were determined experimentally and refined in iso-
tropic approximation.
3,3′-(Biphenyl-4,4′-diyldihydrazono)bis(1,1,1-tri-
fluoropentane-2,4-dione) (IIIa). Yield 54%, orange
powder, sublimes above 250°C (from ethanol). IR
spectrum, ν, cm–1: 3060, 1580 (N–H); 1695 (C=O);
1625, 1505, 1495 (C=N, C=C); 1145–1160 (C–F).
1H NMR spectrum (CDCl3), δ, ppm: 2.67 s (6H, CH3),
19
7.58 m (4H, m-H), 7.70 m (4H, o-H). F NMR spec-
Crystallographic data for compound IIIe.
C36H20F14N4O4, M 838.56, space group Pbc21, ortho-
rhombic crystals with the following unit cell param-
eters: a = 6.354(4), b = 18.932(2), c = 28.775(3) Å; α =
β = γ = 90°; V = 3461.7(8) Å3; Z = 4; λ = 0.71073 Å;
dcalc = 1.609 g/cm3; μ = 0.157 mm–1. Total of 49650 re-
flections were measured, 11488 of which were inde-
pendent and 3017 had I > 2σ(I); 513 parameters were
calculated; 2θmax = 52°, spherical segment –9 ≤ h ≤ 9,
–28 ≤ k ≤ 28, –43 ≤ l ≤ 42; R1 = 0.0801 from reflec-
tions with I > 2σ(I). The complete set of crystallo-
graphic data for compound IIIe was deposited to the
Cambridge Crystallographic Data Center (www.ccdc.-
cam.ac.uk/conts/retrieving.html; CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK; e-mail: deposit@-
ccdc.cam.ac.uk; entry no. CCDC 624129).
trum (CDCl3): δF 91.54 ppm, s. Found, %: C 51.20;
H 3.31; F 22.10; N 10.71. C22H16F6N4O4. Calculated,
%: C 51.37; H 3.14; F 22.16; N 10.89.
2,2′-(Biphenyl-4,4′-diyldihydrazono)bis(4,4,4-tri-
fluoro-1-phenylbutane-1,3-dione) (IIIb). Yield 59%,
mixture of isomers A and B (~10:1), orange powder,
mp >250°C (from ethanol). IR spectrum, ν, cm–1:
3200, 1575 (N–H); 1700 (C=O); 1620, 1600, 1520
(C=N, C=C); 1150–1240 (C–F). 1H NMR spectrum, δ,
ppm: in CDCl3: isomer A: 7.48–7.74 m (18H, Harom),
14.08 br.s (2H, NH); isomer B: 7.91–8.17 m (18H,
H
arom), 14.03 br.s (2H, NH); in DMF-d7: isomer A:
7.59–8.03 m (18H, Harom), 12.75 br.s (2H, NH); isomer
B: 7.74–8.2 m (18H, Harom), 11.69 br.s (2H, NH).
19F NMR spectrum (DMF-d7), δF, ppm: isomer A:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007

SHCHUR et al.
1786
93.92 s (CF3); isomer B: 87.87 s (CF3). Found, %:
C 60.32; H 3.17; F 17.62; N 8.43. C32H20F6N4O4. Cal-
culated, %: C 60.19; H 3.16; F 17.85; N 8.77.
isomer A: 7.47 m (4H, m-H), 7.56–7.62 m (10H, Ph),
7.73 m (4H, o-H), 14.05 br.s (2H, NH); isomer B:
7.40 m (4H, m-H), 7.52–7.69 m (10H, Ph), 8.01 m
(4H, o-H), 14.02 br.s (2H, NH). 19F NMR spectrum
(CDCl3), δF, ppm: isomer A: 37.64 m (4F, 5-F),
49.27 m (4F, 4-F), 81.45 t (6F, 6-F, J = 9.5 Hz); isomer
B: 37.90 m (4F, 5-F), 48.06 m (4F, 4-F), 81.36 t (6F,
6-F, J = 9.5 Hz). Found, %: C 51.68; H 2.21; F 31.76;
N 6.92. C36H20F14N4O4. Calculated, %: C 51.56;
H 2.40; F 31.72; N 6.68.
3,3′-(Biphenyl-4,4′-diyldihydrazono)bis(1,1,1-tri-
fluoro-5,5-dimethylhexane-2,4-dione) (IIIc). The
product was washed with ethanol. Yield 57%, mixture
of isomers A and B (~6 : 5), brown–red powder,
mp 143–145°C. IR spectrum, ν, cm–1: 3120, 1580
(N–H); 1710, 1680 (C=O); 1625, 1515 (C=N, C=C);
1155–1190 (C–F). 1H NMR spectrum (CDCl3), δ, ppm:
isomer A: 1.34 s (18H, t-Bu), 7.53 m (4H, m-H),
7.69 m (4H, o-H), 14.08 br.s (2H, NH); isomer B:
1.43 s (18H, t-Bu), 7.48 m (4H, m-H), 7.67 m (4H,
o-H), 13.78 d (2H, NH, J = 1 Hz). 13C NMR spectrum
(CDCl3), δC, ppm, A: 26.19 [C(CH3)3], 44.73
[C(CH3)3], 117.4 (Cm), 117.5 q (CF3, 1JCF = 292.6 Hz),
128.18 (Co), 129.3 (C2), 138.31 (Ci), 140.40 (Cp),
3,3′-(Biphenyl-4,4′-diyldihydrazono)bis(5,5,6,6,-
7,7,8,8,8-nonafluorooctane-2,4-trione) (IIIf). Yield
77%, yellow powder, mp 185–187°C (from ethanol).
IR spectrum, ν, cm–1: 3060, 1580 (N–H); 1705 (C=O);
1
1630, 1515 (C=N, C=C); 1130–1260 (C–F). H NMR
spectrum (CDCl3), δ, ppm: 2.64 s (6H, CH3), 7.56 m
(4H, m-H), 7.71 m (4H, o-H), 15.33 s (2H, NH).
19F NMR spectrum (CDCl3), δF, ppm: 36.46 m (4F,
7-F), 40.97 m (4F, 6-F), 50.25 m (4F, 5-F), 81.92 t.t
2
176.95 q (COCF3, JCF = 32.1 Hz), 206.41 (COBu-t);
isomer B: 27.83 [C(CH3)3], 43.9 [C(CH3)3], 115.66 q
1
(CF3, JCF = 288 Hz), 117.2 (Cm), 128.32 (Co), 130.67
3
4
(6F, 8-F, J = 10, J = 2.4 Hz). Found, %: C 41.19;
H 1.75; F 41.96; N 6.57. C28H16F18N4O4. Calculated,
%: C 41.29; H 1.98; F 41.99; N 6.88.
(C2), 138.14 (Ci), 140.27 (Cp), 178.04 q (COCF3,
19
2JCF = 37.1 Hz), 203.14 (COBu-t). F NMR spectrum
(CDCl3), δF, ppm: isomer A: 92.03 d.d (CF3, J = 2.2,
0.7 Hz); isomer B: 89.19 d (CF3, J = 1 Hz). Found, %:
C 56.45; H 4.65; F 18.67; N 9.39. C28H28F6N4O4. Cal-
culated, %: C 56.19; H 4.72; F 19.04; N 9.36.
Diethyl 2,2′-(biphenyl-4,4′-diyldihydrazono)bis-
(4,4,4-trifluoro-3-oxobutanoate) (IVa). Yield 51%,
orange powder, mp 210–212°C (from ethanol). IR
spectrum, ν, cm–1: 3140, 1595 (N–H); 1715 (C=O);
1670 (CO, ester); 1535 (C=N, C=C); 1140–1200
(C–F). 1H NMR spectrum (CDCl3), δ, ppm: 1.44 t (6H,
CH2CH3, J = 7.1 Hz), 4.43 q (4H, OCH2, J = 7.1 Hz),
7.51 m (4H, m-H), 7.68 m (4H, o-H), 13.56 br.s
(2H, NH). 13C NMR spectrum (CDCl3), δC, ppm:
14.03 (CH2CH3), 61.98 (OCH2), 117.12 (Cm), 117.13 q
4,4′-(Biphenyl-4,4′-diyldihydrazono)bis(1,1,2,2-
tetrafluorononane-3,5-dione) (IIId). Yield 68%, yel-
low powder, mp 120–121°C (from ethanol). IR spec-
trum, ν, cm–1: 3040, 1575 (N–H); 1705, 1695 (C=O);
1
1640, 1510 (C=N, C=C); 1070–1125 (C–F). H NMR
spectrum (CDCl3), δ, ppm: 0.96 t (6H, CH3, J =
1
(CF3, JCF = 292.7 Hz), 121.55 (C2), 128.17 (Co),
7.3 Hz), 1.42 m and 1.64 m (8H, 7-H, 8-H), 3.02 t (4H,
2
3
4
138.17 (Ci), 140.32 (Cp), 163.74 q (CO2Et, JCF
=
6-H, J = 7.3 Hz), 6.38 t.t (2H, CHF2, J = 53.3, J =
5.5 Hz), 7.54 m (4H, m-H), 7.71 m (4H, o-H), 15.32 s
(2H, NH). 19F NMR spectrum (CDCl3), δF, ppm:
2
19
1 Hz), 174.57 q (COCF3, JCF = 32.7 Hz). F NMR
spectrum (CDCl3): δF 91.3 ppm, d (J = 0.9 Hz). Found,
%: C 50.23; H 3.37; F 19.79; N 9.70. C24H20F6N4O6.
Calculated, %: C 50.18; H 3.51; F 19.84; N 9.75.
2
3
24.92 d.t (4F, HCF2, J = 53.2, J = 7.6 Hz), 42.59 m
(4F, CF2). Found, %: C 54.79; H 4.53; F 22.68; N 8.41.
C30H30F8N4O4. Calculated, %: C 54.38; H 4.56;
F 22.94; N 8.46.
Dimethyl 2,2′-(biphenyl-4,4′-diyldihydrazono)-
bis(4,4,5,5-tetrafluoro-3-oxopentanoate) (IVb). The
product was washed with ethanol. Yield 66%, yellow
powder, mp 200–201°C. IR spectrum, ν, cm–1: 3130,
1580 (N–H); 1715 (C=O); 1670 (C=O, ester); 1610,
2,2′-(Biphenyl-4,4′-diyldihydrazono)bis(4,4,5,5,-
6,6,6-heptafluoro-1-phenylhexane-1,3-dione) (IIIe).
Yield 74%, mixture of isomers A and B (~10:1),
orange powder, mp 180–181°C (from ethanol). IR
spectrum, ν, cm–1: 3080, 1575 (N–H); 1700, 1680 sh
(C=O); 1615, 1600, 1515 (C=N, C=C); 1165–1240
(C–F). IR spectrum (CHCl3), ν, cm–1: 3440, 3050,
1575 (N–H); 1725, 1700, 1680 sh (C=O); 1620, 1600
1
1525 (C=N, C=C); 1220–1250 (C–F). H NMR spec-
trum (CDCl3), δ, ppm: 3.97 s (6H, OCH3), 6.36 t.t (2H,
CHF2, 2J = 53, 3J = 5.5 Hz), 7.50 m (4H, m-H), 7.69 m
(4H, o-H), 13.55 s (2H, NH). 19F NMR spectrum
2
3
(CDCl3), δF, ppm: 24.35 d.t (4F, HCF2, J = 53, J =
1
(C=N, C=C). H NMR spectrum (CDCl3), δ, ppm:
7.3 Hz), 42.28 m (4F, CF2). Found, %: C 47.31;
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007

SYNTHESIS, STRUCTURE, AND COMPLEXING ABILITY
1787
H 2.87; F 24.84; N 9.20. C24H18F8N4O6. Calculated, %:
C 47.22; H 2.97; F 24.90; N 9.18.
Bis[2,2′-(biphenyl-4,4′-diyldihydrazono)bis-
(4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-di-
onato-O,N)]dicopper(II) (VIb). The product was
washed with hot ethanol. Yield 84%, dark green
powder, mp 342–343°C. IR spectrum, ν, cm–1: 1685 sh,
1670 (C=O); 1600, 1580, 1510, 1490 (C=N, C=C);
1190–1230 (C–F). Found, %: C 47.99; H 2.24;
F 28.98; N 6.19. C72H36Cu2F28N8O8. Calculated, %:
C 48.04; H 2.02; F 29.55; N 6.22.
Diethyl 2,2′-(biphenyl-4,4′-diyldihydrazono)bis-
(4,4,5,5,6,6,6-heptafluoro-3-oxohexanoate) (IVc).
Yield 71%, yellow powder, mp 144–146°C (from
ethanol). IR spectrum, ν, cm–1: 3120, 1580 (N–H);
1710 (C=O); 1670 (C=O, ester); 1615, 1595, 1530
1
(C=N, C=C); 1210–1240 (C–F). H NMR spectrum
(CDCl3), δ, ppm: 1.44 t (6H, CH2CH3, J = 7.1 Hz),
4.42 q (4H, OCH2, J = 7.1 Hz), 7.49 m (4H, m-H),
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 05-03-32384a) and by the Program for State
Support of Leading Scientific Schools (project
no. 9178.2006.3).
19
7.68 m (4H, o-H), 13.60 s (2H, NH). F NMR spec-
trum (CDCl3), δF, ppm: 37.52 m (4F, 5-F), 49.43 m
(4F, 4-F), 81.41 t (6F, 6-F, J = 9.5 Hz). Found, %:
C 43.45; H 2.42; F 34.32; N 7.28. C28H20F14N4O6. Cal-
culated, %: C 43.42; H 2.60; F 34.34; N 7.23.
REFERENCES
Dimethyl 2,2′-(biphenyl-4,4′-diyldihydrazono)-
bis(4,4,5,5,6,6,7,7,7-nonafluoro-3-oxoheptanoate)
(IVd). The product was washed with ethanol. Yield
73%, yellow powder, mp 190–192°C. IR spectrum, ν,
cm–1: 3150, 1580 (N–H); 1700 (C=O); 1680 (C=O,
ester); 1615, 1515 (C=N, C=C); 1135–1230 (C–F).
1H NMR spectrum (CDCl3), δ, ppm: 3.96 s (6H,
OCH3), 7.50 m (4H, m-H), 7.69 m (4H, o-H), 13.58 s
(2H, NH). 19F NMR spectrum (CDCl3), δF, ppm:
36.47 m (4F, 6-F), 40.86 m (4F, 5-F), 50.02 t (4F, 4-F,
1. Ovcharenko, V.I. and Sagdeev, R.Z., Usp. Khim., 1999,
vol. 68, p. 381.
2. Burgart, Ya.V., Fokin, A.S., Kuzueva, O.G., Chupa-
khin, O.N., and Saloutin, V.I., J. Fluorine Chem., 1998,
vol. 92, p. 101; Khudina, O.G., Burgart, Ya.V., Salou-
tin, V.I., and Chupakhin, O.N., J. Fluorine Chem., 2004,
vol. 125, p. 401; Khudina, O.G., Shchegol’kov, E.V.,
Burgart, Ya.V., Saloutin, V.I., and Chupakhin, O.N.,
J. Fluorine Chem., 2004, vol. 125, p. 1363; Khudi-
na, O.G., Shchegol’kov, E.V., Burgart, Ya.V., Salou-
tin, V.I., Bukhvalov, D.V., Starichenko, D.V., Shvach-
ko, Yu.N., Korolev, A.V., Ustinov, V.V., Aleksand-
rov, G.G., Eremenko, I.L., Kazheva, O.N., Shilov, G.V.,
D’yachenko, O.A., and Chupakhin, O.N., Izv. Ross. Akad.
Nauk, Ser. Khim., 2007, no. 1, p. 103.
3. Kazitsyna, L.A. and Kupletskaya, N.B., Primenenie UF-,
IK-, YaMR- i mass-spektroskopii v organicheskoi khimii
(Application of UV, IR, NMR, and Mass Spectroscopy in
Organic Chemistry), Moscow: Mosk. Gos. Univ., 1979,
pp. 213, 216.
4. Khudina, O.G., Shchegol’kov, E.V., Burgart, Ya.V., Ko-
dess, M.I., Saloutin, V.I., Kazheva, O.N., Shilov, G.V.,
D’yachenko, O.A., Grishina, M.A., Potemkin, V.A., and
Chupakhin, O.N., Russ. J. Org. Chem., 2007, vol. 43,
p. 380.
3
J = 12 Hz), 80.88 t.t (6F, 7-F3, J = 9.5, 4J = 2.3 Hz).
Found, %: C 39.75; H 2.04; F 40.65; N 6.64.
C28H16F18N4O6. Calculated, %: C 39.73; H 1.91;
F 40.4; N 6.62.
2,2′-(Biphenyl-4,4′-diyldihydrazono)bis(4,4,5,5,-
6,6,6-heptafluoro-1-phenylhexane-1,3-dione) (IIIe)
nickel and copper complexes VIa and VIb (general
procedure). A solution of 1 mmol of ligand IIIe in 4 ml
of DMF was heated to 60°C, a solution of 1 mmol of
nickel(II) or copper(II) acetate (Va or Vb) in 16 ml of
methanol was added, and a solution of 10 mg of so-
dium acetate in 2 ml of water was then added drop-
wise. The mixture was stirred for 8 h at 80–90°C, and
the precipitate was filtered off and washed with water.
Bis[2,2′-(biphenyl-4,4′-diyldihydrazono)bis-
(4,4,5,5,6,6,6-heptafluoro-1-phenylhexane-1,3-di-
onato)-O,N]dinickel(II) (VIa). Yield 91%, yellow–
brown powder, mp >360°C (from methanol). IR spec-
trum, ν, cm–1: 1665 sh, 1650 (C=O); 1600, 1580, 1530
(C=N, C=C); 1180–1230 (C–F). Found, %: C 48.70;
H 2.31; F 29.44; N 6.50. C72H36F28N8Ni2O8. Calculat-
ed, %: C 48.30; H 2.03; F 29.71; N 6.26.
5. Sinyaev, A.A., Grishina, M.A., and Potemkin, V.A.,
Arkivoc, 2004, part (xi), p. 43.
6. Krishnankutty, K. and Rena, V.T., Synth. React. Inorg.
Met.-Org. Chem., 1995, vol. 25, p. 243; Krishnankutty, K.
and Michael, J., Indian J. Chem., Sect. A, 1995, vol. 34,
p. 299.
7. Scheldrik, G.M., SHELXS 97 and SHELXL 97, Gottingen:
Univ. of Gottingen, 1997.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 12 2007