Synthesis and NMR study of cyclohexylphosphonates

Article abstract of DOI:10.1134/S1070363211030066

Cyclohexyl-, 2-chlorocyclohex-1-yl and cyclohexen-1-ylphosphonic acids chlorides and fluorides were synthesized and studied by the ¹H, ¹³C, ¹⁹F, and ³¹P NMR methods with the use of correlation spectroscopy and q

Full text of DOI:10.1134/S1070363211030066

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 481–487. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © K.S. Titov, V.I. Zakharov, M.N. Krivchun, B.I. Ionin, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 3, pp. 384–
390.
Synthesis and NMR Study of Cyclohexylphosphonates
K. S. Titov, V. I. Zakharov, M. N. Krivchun, and B. I. Ionin
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
е-mail: e-mail:borisionin@mail.ru
Received October 5, 2010
Abstract—Cyclohexyl-, 2-chlorocyclohex-1-yl and cyclohexen-1-ylphosphonic acids chlorides and fluorides
1
were synthesized and studied by the H, 13C, 19F, and 31P NMR methods with the use of correlation
spectroscopy and quantum-chemical calculations.
DOI: 10.1134/S1070363211030066
Phosphorus-substituted derivatives of cyclohexane
remain virtually unexplored compounds as concerns of
the methods for their synthesis, chemical properties,
and the spatial structure. Meanwhile the compounds of
this class are of great practical use, in particular, 1-
(butyl-amino)cyclohexylphosphonic acid dibutyl ester
(trake-fon, buminafos) is applied as phytohormone [1,
2], and phosphorus-containing derivative of
cyclohexene, 3-(pentyl-3-hydroxy)-4-acetylamino-5-
aminocyclohexen-1-ylphosphonic acid ammonium salt
(tamiphosphor), is the antiviral drug [3, 4].
POX2
POX2
Cl
POX2
I, IV
II, V
III, VI
X = Cl (I, II, III), F (IV, V, VI).
Methods of the synthesis of cyclohexane deriva-
tives with a C–P bond are limited. The sufficiently
effective method is based on the addition reaction of
hydrophosphoryl compounds to the C=O bond of
cyclohexanone and its derivatives, which has been
recently modified by O.O. Kolodyaznaya and
O.I. Kolodyazhnyi [5].
The aim of this work is the synthesis of the simplest
phosphorus derivatives of cyclohexane and their examina-
tion by means of NMR spectroscopy to determine the
spectroscopic characteristics, which are necessary of
the study of the related more complicated structures.
Use of cyclohexyl-containing Grignard reagents [3]
has the limitations of organometallic synthesis. Cyclo-
hexylphosphonate was obtained starting from cyclo-
hexane via the reaction of oxidative chlorophos-
phorylation [6]. Although this method is ineffective for
processing because of the considerable consumption of
phosphorus trichloride in a parallel reaction of oxida-
tion to the oxychloride, it is sufficiently convenient for
the syntheses for research purposes, because it allows
to obtain phosphonic acids dichlorides, the suitable
synthons for subsequent conversion into other
derivatives, through one stage using the available
materials.
Unfortunately, the use of the proton magnetic re-
sonance spectroscopy to study the cyclohexane com-
pounds has limitations related to the fact that the
signals are located in a narrow spectral region, and the
spectra are difficult for interpretation due to the
complex spin-spin interactions. Much the same applies
to the 13C NMR spectroscopy.
In this regard, the spectral analysis of phosphorus-
containing cyclohexane derivatives is of particular
interest because of the possibility of obtaining addi-
tional spectroscopic parameters and application of
heteronuclear spectroscopy. In this study the cyclo-
hexane derivatives such as cyclohexyl- (I, IV), 2-chloro-
cyclohexyl- (II, V) and cyclohexen-1-ylphosphonic
acids (III, VI) dichlorides and difluorides were syn-
thesized and studied.
POCl2
POF2
PCl3, O2
ZnF2
481

482
TITOV et al.
We have shown previously [7] that the formation of
the C–P bond via the oxidative chlorophosphorylation
of unsaturated hydrocarbons begins with a chlorine
radical attack on the double bond that determines the
regioselectivity of this process. This method is used in
the present work for the synthesis of compounds II–IV.
POCl2
POCl2
PCl3, O2
Et3N
Cl
III
II
V
ZnF2
ZnF2
POF2
POF2
Cl
VI
The structure and individuality of the obtained
cyclohexylphosphonic dichlorides and difluorides were
proved by the Н, С, F, and P NMR spectroscopy
contains two signals of the fluorine nuclei, which are
the doublets of doublets due to the spin-spin coupling
of nuclei 19F–31P and 19F–19F. The vicinal constant 2JFF
in such systems 19F–31P–19F was apparently first ob-
tained. Its value is 108.4 Hz.
1
13
19
31
(Table 1).
Chemical shifts of the phosphorus nuclei of com-
pounds I–VI are characteristic of the corresponding
saturated and unsaturated derivatives. In the spectra of
To verify these data, we performed quantum-
chemical calculations for compounds IV–VI by
RB3LYP/6-31+G(d) method using full geometry
optimization. These calculations showed that the
predominant conformation of the cyclohexane
derivatives IV and VI is the chair conformation with
the equatorial location of C–P bond, while in all
compounds the minimum energy corresponds to a
skewed-staggered conformation of difluorophosphoryl
group relative to this bond. This leads to the fluorine
atoms non-equivalence. In the spectra this non-equi-
valence is detected only in the case of 2-choro deriva-
tive VI, where the rotation of the difluorophosphoryl
difluorides IV and VI the phosphorus resonates as a
1
triplet signal with the characteristic constants JPF
≈
1000 Hz. Accordingly, the 19F nuclei signals are
doublets with the constant JPF of the same value. In
1
contrast to these compounds the 31P NMR spectrum of
chlorocyclohexyl derivative V contains two doublets,
which indicates some non-equivalence of the fluorine
nuclei. This may be due to the predominance of
conformation which is unsymmetrical relative to the
cyclohexane ring with respect to the C–P bond.
Accordingly, the 19F NMR spectrum of compound V
Table 1. Parameters of the 31P, 13C, and 19F NMR spectra for compounds I–VI
Comp.
δP, ppm (JPF, Hz)
56.94
δF, ppm (JPF, Hz)
δC, ppm (JCP, JCF, Hz)
no.
25.24 d (3JСP 4.63), 25.82 d (2JСP 10.17), 50.95 (1JСP 93.11)
26.06 d (3JСP 4.29), 35.87 d (2JСP 11.02), 57.45 d (1JСP 77.71)
I
49.93
36.08
II
21.46 d (3JСP 12.68), 23.41 d (3JСP 11.93), 26.19 d (2JСP 20.74), 134.10 d (1JСP
135.63), 146.81 d (2JСP 9.06)
III
25.67 t (1JPF 1156.01) 99.87 d (1JFР 1156.01) 32.89 d.t (1JСP 139.16, 2JСF 15.10)
21.69 t (1JPF 1146.8) 99.93 d (1JFР 1146.8) 23.66 d (3JСP 15.75), 25.72 d (3JСP 4.93), 36.41 d (2JСP 14.19), 43.16 d (1JСP
104.63 d (1JFР 1146.8) 143.54, 2JСF 15.90), 55.50 d (2JСP 6.84)
IV
V
11.71 t (1JPF 1101.09) 100.92 d (1JFР 1101.09) 21.23 d (3JСP 11.93), 23.44 d (3JСP 10.32), 26.36 d (2JСP 21.14), 121.11 d.t
VI
(2JСP 193.71, 3JСF 25.16), 151.90 d (1JСP 9.51)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

483
position with approximately the same value of the
SYNTHESIS AND NMR STUDY OF CYCLOHEXYLPHOSPHONATES
moiety around the C–P bond is apparently more
hindered.
3
2
constant: J2(6)a,3(5)a ≈3J2(6)a,1a ≈ J2(6)a,2(6)e ≈3J2(6)a,Pe1
≈
1
12.6 Hz. The interaction of these protons with the
vicinal equatorial protons leads to a triplet splitting of
each of the major peaks (J ≈ 3.4 Hz).
The H NMR spectra of cyclohexylphosphonic di-
chlorides and difluorides I and II correspond to the
symmetric structure of the ring. The proton spectrum
of dichloride I (700 MHz) (Fig. 1) contains a well-
separated signals of the protons Ha1, Ha2,6, He2,6, Ha3,5,
He3,5, Ha4 and He4. All signals are in the range of 1–
2.5 ppm (~1000 Hz when the spectra are recorded at
700 MHz). The assignment is done based on the
analysis of the chemical shifts and spin-spin coupling
constant with accounting for the ring geometry in a
chair conformation with an equatorial location of
dichlorophosphonate group in the position 1. The
integral intensity is somewhat distorted because of the
overlap of closely located signals. However, in general
it is in agreement with the given assignement.
The proton He4 signal (Fig. 1d) consists of a main
doublet with the splitting ~12.6 Hz, due to, obviously,
the spin-spin coupling with the geminal proton Ha4.
Each of the components of the doublet is a multiplet
(apparently, close to quintet) due to the interaction
with the axial and equatorial protons in positions 3 and
5, with approximately equal coupling constants
(~3 Hz), which is consistent with the mentioned above
analysis of the axial protons signals.
Thus, the 1H NMR spectrum data (700 MHz) along
with the results of quantum-chemical calculations
indicate the existence of cyclohexylphosphonic di-
halides in a sufficiently rigid chair configuration with
an equatorial location of the phosphonate group.
The 1H NMR spectrum of difluoride IV (400 MHz)
is generally similar to that of dichloride, except for the
presence of an additional triplet splitting of the signal
components of the proton in position 1 due to the spin-
spin coupling with the nuclei 19F (3JHF 3.04 Hz).
Unfortunately, the 13C NMR spectra of these
compounds (50.3 and 100.5 MHz for difluoride IV and
dichloride I, respectively) (Fig. 2) do not allow us to
obtain the characteristics of the carbon atoms
resonance due to the proximity of the signals (within
0.5 ppm) of all the carbon nuclei except for the ipso-
carbon. The signal of ipso-carbon of dichloride I is a
doublet at δC 50.95 ppm (1JCP 93.11 Hz). In the
spectrum of difluoride IV the signal of the ipso-carbon
atom is shifted upfield (δC 32.89 ppm, 1JCP 139.16, 2JCF
15.10 Hz). The signals of other carbon atoms of
compounds I and IV are located in a narrow region δC
from 24.5 to 25.2 ppm.
As is known, the value of vicinal spin–spin coupl-
ing constant depends essentially on the value of the
dihedral angle HCCH. For cyclohexane derivatives, in
general and according to the quantum-chemical
calculations, the dihedral angle HaCCHa is close to
180º, so that this constant is maximal. Accordingly, the
constants HaCCHe and HeCCHe should be small since
the corresponding dihedral angles are close to 60º.
Consequently, it is expected that the signals of axial
protons must be better resolved in the spectrum. In the
spectrum of compound I (Fig. 1) the proton signal Ha1,
which is a quartet of triplets, is more resolved.
Obviously, the signal type corresponds to equal spin–
spin coupling constants this nucleus with the protons
Ha2,6 and with the 31P nucleus: 3J1a,2(6)a = 2J1a,P = 12.3 Hz,
3J1a,2(6)e = 3.1–3.2 Hz.
A similar analysis of the axial proton signal in
position 4 indicates the equality of proton–proton
constants: 3J4a,3(5)a = 2J4a,4e = 12.8 Hz, 3J4a,3(5)e = 3.4 Hz.
Assignment of the signals of axial protons in
positions 2,6 and 3,5 can be made on the basis of the
analysis of their multiplicity. The Ha3,5 proton signal
located as expected in a stronger field contains four
main peaks separated by 6.12 Hz from each other,
indicating that these protons are neighboring to the
proton Ha4 and the approximate equality of the two
1
The correlation NMR spectrum H–13С HMQC-2
(Jeol 400/100 MHz spectrometer) also did not possess
significant information because of the proximity of
signals of all the carbon atoms except the ipso-carbon.
By the cross-peaks only the accordance of the ipso-
carbon and the proton connected to it can be identified.
vicinal and one geminal constants [3J4a,3(5)a ≈ 3J2(6)a,3(5)a
2J3(5)a,3(5)e ≈ 12.6 Hz].
≈
1
The parameters of H, 13C, 31P, and 19F NMR spectra
of I and IV are shown in Tables 1 and 2, the 13C NMR
spectra of compounds I and IV are shown in Fig. 2.
In contrast, the signal of the protons Ha2,6 contains
5 main peaks separated also by 12.6 Hz. The increase
in the multiplicity is clearly associated with the vicinal
spin–spin coupling with 31P nucleus in the equatorial
In contrast to the compounds I and IV, the quan-
tum-chemical calculations of geometry of cyclohexen-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

484
TITOV et al.
(a)
δ, ppm
(c) На4
На1
(b)
δ, ppm
δ, ppm
(e) На3,5
На2,6
(d)
δ, ppm
δ, ppm
Не4
(f)
δ, ppm
Fig. 1. (a) 1Н NMR spectrum of dichloride I (700 MHz, CDCl3) and (b–f) its components on an enlarged scale.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011

485
SYNTHESIS AND NMR STUDY OF CYCLOHEXYLPHOSPHONATES
(a) (b)
δС, ppm
δС, ppm
Fig. 2. 13С NMR spectrum of (a) dichloride I and (b) difluoride IV (50 MHz, CDCl3).
1-ylphosphonic acid difluoride VI indicates the planar
structure of the ring. The proton resonance spectrum of
the corresponding dichloride III (Fig. 3) agrees with
this conclusion. The spectrum contains a doublet signal
with a chemical shift of 6.85 ppm, corresponding to
the proton H2 at the double bond with a spin–spin
We failed to obtain reliable spectral characteristics
for 1H and 13C nuclei of other compounds studied.
Thus, we synthesized and studied the structure of
phosphorus-containing derivatives of cyclohexane:
cyclohexyl- (I, IV), 2-chlorocyclohexyl- (II, V), and
cyclohexen-1-ylphosphonic (III, VI) dichlorides and
difluorides.
2
coupling constant JHP 29.21 Hz characteristic of the
cis-proton-phosphorus interaction, with the intensity
corresponding to one proton. The signal with an
intensity of about 4 protons in the region of 2.13–
2.14 ppm obviously corresponds to the resonance of
4 hydrogen nuclei in the allylic positions, H3 and H6.
Two signals in the stronger field at δ 1.5 and 1.6 ppm
probably correspond to the hydrogen atoms H4 and H5,
which are the most distant from the double bond. We
assign the most upfield signal to the proton H5, which
is the most distant from the phosphorus-containing
group. But this correlation is ambiguous because of the
proximity of the chemical shifts of nuclei H4 and H5.
The signals are weakly split. The maximal value of the
spin–spin coupling between the protons in this
molecule is 4.4 Hz, i.e. there is no interaction of axial–
axial type, which is consistent with the structure of the
molecule, close to planar.
EXPERIMENTAL
The NMR spectra were recorded on spectrometers
Bruker AC-200 [200.132 (1H), 50.328 (13C), 81.014 MHz
(31P)], Bruker AC-400 [400.133 (1H), 376.506 MHz
(19F)], Varian S-700 [699.75 MHz (1H)], and Tesla
BS-497 [100 MHz, using the double magnetic
resonance H–{31P}]. The two-dimensional correlation
1
spectra were recorded on a HMQC Jeol JNM-
The 13C NMR spectrum of dichloride VI contains 6
signals of the ring carbon atoms, of which 5 are split
into doublets because of spin–spin interaction with the
31P nucleus. Based on the analysis of chemical shifts,
we assign these signals as follows:
Carbon
δ, ppm
C1
C2
C3
C4
C5
C6
atom
δC, ppm 134.10 146.81 23.40 20.58
21.47 26.19
12.68 20.73
Fig. 3. 1Н NMR spectrum of dichloride III (400 MHz,
J
CP, Hz 135.63
9.06 11.93
0
CDCl3).
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486
TITOV et al.
Table 2. Signals assignment in the 1H NMR spectrum (700 MHz) of I
Atom
Ha1
δ, ppm
2.39
1.50
1.91
1.32
2.20
1.24
1.74
Geminal constants, 2J, Hz
2J1a,P 12.3
Vicinal constants, 3J, Hz
3J1a,2(6)e 3.1–3.2, 3J1a,2(6)a 12.3
3J2a,3a 12.4, 3J2a,3e 3.5, 3J2a,P 12.4
3J2e,P 13.1, 3J2(6)e,1a 3.1–3.2
3J3a,2a 12.4, 3J3a,4a 12.4
Ha2,6
Hе2,6
Ha3,5
Hе3,5
Ha4
2J2a,2e 9.6
2J2a,2e 9.6
2J3a,3e 9.7
2J3a,3e 9.7
3J3е,2а 3.5, 3J3е,4а 3.4
2J4a,4e 12.4
3J4a,3a 12.4, 3J4a,3e 3.4
Hе4
2J4a,4e 12.4
ECX400A instrument. Hexamethyldisiloxane (HMDS)
was used as an internal reference for H NMR spectra.
Cyclohex-1-enylphosphonic dichloride (III). To a
solution of 10 g of II in 20 ml of anhydrous diethyl
ether was added a solution of 5 g of triethylamine in
10 ml of anhydrous diethyl ether at cooling. The
reaction mixture was kept for 0.5 h under cooling and
1 h at room temperature. Then triethylamine salt was
filtered off, the filtrate was concentrated and
fractionated. Fraction with bp 112–114°С (4 mm Hg)
was collected. Yield 4.4 g (52%), colorless liquid, bp
1
Phosphorus chemical shifts were determined relative to
external 85% phosphoric acid (Bruker AC-200) and
trimethylphosphate (Tesla BS-497). The 13C spectra
were taken relative to internal CDCl3 and DMSO-d6.
The standard laboratory techniques were used to purify
and dry the organic solvents and reagents [8–10].
A general procedure for the synthesis of
dichlorides (I, II). A reactor was charged with a
substrate and 5-fold excess of phosphorus trichloride.
Dry oxygen was passed through the reaction mixture
under stirring and cooling, while maintaining the
temperature below 15°C. As the exothermal process
completed, the formed POCl3 was removed, and the
residue was fractionated under the reduced pressure.
1
82–84°C (<1 mm Hg). Н NMR spectrum (400 MHz,
CDCl3), δН, ppm: 1.48–1.49 m (2Н, Н4), 1.56–1.59 m
2
(2Н, Н5), 2.13–2.14 m (4Н, Н3,6), 6.85 d (1Н, Н2, JHP
29.21 Hz). 13С NMR spectrum (50 MHz, CDCl3), δС,
ppm: 20.58 (С4), 21.46 d (С5, 3JСP 12.68 Hz), 23.41 d
(С3, 3JСP 11.93 Hz), 26.19 d (С6, 2JСP 20.74 Hz), 134.10
d (С1, 1JСP 135.63 Hz), 146.81 d (С2, 2JСP 9.06 Hz). 31Р
NMR spectrum (81 MHz, CDCl3): δР 36.08 ppm.
Cyclohexylphosphonic dichloride (I). Yield 21.6 g
(45%), colorless liquid, bp 104–106°C (4 mm Hg). Н
A general procedure for the synthesis of
difluorides (IV, V, VI). The corresponding dichlo-
rides (I, II, III) were distilled under the reduced
pressure over two-fold amount of the freshly calcined
ZnF2 followed by the repeated fractionating under the
reduced pressure.
1
NMR spectrum (400 MHz, CDCl3), δН, ppm: 1.11–
1.31 m (3Н, На4, На3,5), 1.37–1.39 m (2Н, На2,6), 1.65–
1.69 m (1Н, Не4), 1.81–1.88 m (2Н, Не2,6), 2.10–2.15 m
(2Н, Не3,5), 2.33 q.t (1Н, На1, JHP 11.60, 3JHH 2.80 Hz).
2
13С NMR spectrum (50 MHz, CDCl3), δС, ppm: 25.24
3
2
d (С3,5, JСP 4.63 Hz), 25.82 d (С2,6, JСP 10.17 Hz),
Cyclohexylphosphonic difluoride (IV). Yield 1.51 g
25.83 (С4), 50.95 d (С1, JСP 93.11 Hz). 31Р NMR
(59.8%), colorless liquid, bp 57–59°C (4 mm Hg). Н
1
1
spectrum (81 MHz, CDCl3): δР 56.94 ppm.
NMR spectrum (400 MHz, CDCl3), δН, ppm: 1.06–
1.20 m (3Н, На4, На3,5), 1.26–1.37 m (2Н, На2,6), 1.53–
1.56 m (1Н, Не4), 1.62–1.72 m (2Н, Не2,6), 1.85 t (2Н,
2-Chlorocyclohexylphosphonic dichloride (II).
Yield 30.1 g (42%), colorless liquid, bp 115–116°C
Не3,5, JHH 8.80 Hz), 1.95–2.08 m (1Н, На1). 13С NMR
2
1
(<1 mm Hg). Н NMR spectrum (400 MHz, CDCl3),
spectrum (50 MHz, CDCl3), δС, ppm: 24.62–25.14 m
δН, ppm: 1.34–1.38 m (2Н, Н4), 1.64–2.02 m (4Н,
Н5,6), 2.69–2.85 m (1Н, Н1), 4.23–4.30 m (1Н, Н2). 13С
NMR spectrum (50 MHz, CDCl3), δС, ppm: 23.49
1
2
(С2–6), 32.89 d.t (С1, JСP 139.16, JСF 15.10 Hz). 31Р
NMR spectrum (81 MHz, CDCl3), δР, ppm: 25.67 t
(1JPF 1156.01 Hz). 19F NMR spectrum (376 MHz,
CDCl3), δF, ppm: 99.87 d (1JFР 1156.01 Hz).
3
(С4), 23.73 (С5), 26.06 d (С3, JСP 4.29 Hz), 35.87 d
2
1
(С6, JСP 11.02 Hz), 56.42 (С2), 57.45 d (С1, JСP
77.71 Hz). 31Р NMR spectrum (81 MHz, CDCl3): δР
49.93 ppm.
2-Chlorocyclohexylphosphonic difluoride (V).
Yield 2.56 g (59%), colorless liquid, bp 65–67°C
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SYNTHESIS AND NMR STUDY OF CYCLOHEXYLPHOSPHONATES
1
(<1 mm Hg). Н NMR spectrum (400 MHz, CDCl3),
Pedagogical University) for taking the two-dimen-
sional correlation spectra.
δН, ppm: 1.21–1.39 m (2Н, На5,4), 1.55–1.67 m (2Н,
На3,6), 1.71–1.84 m (2Н, Не4,5), 2.06–2.16 m (1Н, Не6),
2.20–2.30 m (Не3), 2.38–2.49 m (На ), 3.98–4.06 m
1
REFERENCES
(На2). 13С NMR spectrum (50 MHz, CDCl3), δС, ppm:
23.66 d (С5, JСP 15.75 Hz), 24.66 (С4), 25.72 d (С3,
3
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2
3JСP 4.93 Hz), 36.41 d (С6, JСP 14.19 Hz), 43.16 d.t
1
2
2
(С1, JСP 143.54, JСF 15.90 Hz), 55.50 d (С2, JСP
6.84 Hz). 31Р NMR spectrum (81 MHz, CDCl3), δР,
ppm: 21.69 t (1JPF 1146.8 Hz). 19F NMR spectrum
(376 MHz, CDCl3), δF, ppm: 99.93 d (1JFР 1146.8 Hz),
104.63 d (1JFР 1146.8 Hz).
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(4 mm Hg). 1Н NMR spectrum (400 MHz, CDCl3), δН,
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2
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(50 MHz, CDCl3), δС, ppm: 20.60 (С4), 21.23 d (С5,
3JСP 11.93 Hz), 23.44 d (С3, JСP 10.32 Hz), 26.36 d
3
6. Soborovskii, L.Z., Zinoviev, Yu.M., and Englin, M.A.,
(С6, JСP 21.14 Hz), 121.11 d.t (С2, JСP 193.71, JСF
25.16 Hz), 151.90 d (С1, 1JСP 9.51 Hz). 31Р NMR spec-
trum (81 MHz, CDCl3): δР 11.71 t (1JPF 1101.09 Hz).
19F NMR spectrum (376 MHz, CDCl3), δF, ppm:
100.92 d (1JFР 1101.09 Hz).
2
2
3
Dokl. Akad. Nauk SSSR, 1949, vol. 67, p. 293.
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ACKNOWLEDGMENTS
9. Preparativnaya organicheskaya khimiya (Practical
Organic Chemistry), Vul’fson, N.S., Ed., Moscow:
Khimiya, 1964.
The authors are grateful to A.N. Skvortsov (St.
Petersburg State Polytechnical University) for
registration of the spectra on a spectrometer Varian S-
700 operating at 700 MHz, and S.V. Makarenko (The
Collective Instrumetal Center, Herzen Russian State
10. Obshchii praktikum po organicheskoi khimii (Organic
Chemistry Laboratory Guide), Kost, A.N., Ed.,
Moscow: Mir, 1965.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 3 2011