N-(R-cyclopropyl)fluorobenzimidoyl phosphonates

Article abstract of DOI:10.1134/S1070363215020115

Reaction of N-(R-cyclopropyl)benzimidoyl chloride with triethyl phosphite has yielded the corresponding N-(R-cyclopropyl)-substituted benzimidoyl phosphonates existing predominantly in the E-configuration [E: Z ≈ (8-10): 1] at room temperature. ¹⁹

Full text of DOI:10.1134/S1070363215020115

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 2, pp. 418–423. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © P.P. Onys’ko, D.V. Klyukovskii, A.V. Bezdudnyi, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 2, pp. 245–250.
To the 80th Anniversary of B.I. Ionin
N-(R-Cyclopropyl)fluorobenzimidoyl Phosphonates
P. P. Onys’ko, D. V. Klyukovskii, and A. V. Bezdudnyi
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, ul. Murmanskaya 5, Kiev, 02094 Ukraine
e-mail: onysko@rambler.ru
Received December 15, 2014
Abstract—Reaction of N-(R-cyclopropyl)benzimidoyl chloride with triethyl phosphite has yielded the
corresponding N-(R-cyclopropyl)-substituted benzimidoyl phosphonates existing predominantly in the E-
configuration [E : Z ≈ (8–10) : 1] at room temperature. 19F NMR spectroscopy allowed determination of
inductive and resonance σ-constants of N-(R-cyclopropyl)-substituted imidoyl chloride and imidoyl phos-
phonate groups for the first time.
Keywords: imidoyl phosphonate, imidoyl chloride, cyclopropyl, E/Z-isomerism, σ-constant
DOI: 10.1134/S1070363215020115
Imidoyl phosphonates (esters of iminophosphonic
acids) have been a scarcely studied type of imines
[1–3]. At the same time, the presence of “oxidized”
fragment of α-aminophosphonic acid [>P(O)C=N]
capable of reductive modification opens a wide range
of applications of these compounds for synthesis of a
variety of biologically important aminophosphonic
acid derivatives. Being the phosphorus analogs of
natural amino acids, such derivatives have revealed a
complex of practically important properties [4, 5]: they
may act as enzyme regulators and HIV-protease
inhibitors, and have been hence intensively studied.
The majority of synthetic routes leading to amino-
phosphonates I include a key stage of phosphites addi-
tion non-phosphorylated imine II. We have proposed
another synthetic strategy; in contrast to conventional
preparations via the Kabachnik–Fields and the Pudovik
reactions, it uses C-phosphorylated imines III as
starting compounds (Scheme 1) [3, 6–8]. This approach
extends the synthetic possibilities: in particular,
phosphonyl group additionally activates the C=N bond
allowing for the modification under milder conditions.
Moreover, starting from one and the same imidoyl
phosphonate III it is possible to obtain a variety of
acyclic and heterocyclic derivatives bearing an
aminophosphoryl fragment.
We have earlier elaborated methods to prepare NН-,
N-alkyl-, N-acyl-, N-phosphoryl-, and N-sulfonyl-
imidoyl phosphonates and demonstrated their applica-
tion in synthesis of biologically important phosphorus
analogs of amino acids [1, 2, 8, 9]. In this regard, the
compounds containing cyclopropyl group are promis-
ing. The presence of rigid three-membered ring
significantly limits the conformation lability of the
molecule. The compounds modification via introduc-
tion of the strained cyclic fragments has been
recognized among efficient approaches of modern
medicinal chemistry [10]. We have recently prepared
the first representatives of the N-cyclopropyltrifluoro-
acetimidoyl phosphonates family [11]. In this work we
describe a synthetic approach to prepare fluoro-
substituted benzimidoyl phosphonates containing
cyclopropyl substituent at the nitrogen atom; electronic
Scheme 1.
P(OR')2
O
X
R
(R'O)2 P
R
O
N Y
(R'O)2POH
XH
N Y
Y
N
а
R
b
X
H
I
II
III
418

419
N-(R-CYCLOPROPYL)FLUOROBENZIMIDOYL PHOSPHONATES
Scheme 2.
R
ArCOCl
R
R
R
Vа, Vb
SOCl2
P(OEt)3
N
Ar
N
Ar
HN
Ar
NH2
P
OEt
OEt
VIIIа−VIIId
O
Cl
VIIа−VIId
O
IVа, IVb
VIа−VId
IV: R = H (а), CF3 (b); V: Ar = 4-FC6H4 (а), 3-FC6H4 (b); VI–VIII: R = H, Ar = 4-FC6H4 (а); R = CF3, Ar = 4-FC6H4 (b);
R = H, Ar = 3-FC6H4 (c); R = CF3, Ar = 3-FC6H4 (d).
structure of the imidoyl phosphonate group was
studied and some properties of the prepared
phosphorylated imines were studied.
Е/Z-isomers at room temperature; furthermore, we
have elucidated the NMR spectral features allowing
for discrimination of the isomers [12, 14, 15]. In
particular, NH-, N-alkyl-, and N-aryltrifluoro-
acetimidoyl phosphonates exist predominantly in the
Z-form [Z : E ≈ (6–10) : 1] [14, 15], whereas the E-
form is favorable in the case of the studied benz-
imidoyl phosphonates [12, 16, 17]. The investigations
have revealed that 31P NMR spectroscopy is the most
convenient method of structure elucidation of the
isomeric benzimidoyl phosphonates. The phosphorus
nuclei chemical shift of Е-isomers of imidoyl
phosphonates VIII (δР 6.6–7.1 ppm) are shifted
downfield as compared to these of the corresponding
Z-isomers (δР 2.6–3.1 ppm). A notable difference of
13C NMR spectra of the Е- and Z-isomers is the value
of spin-spin interaction constant of the cyclopropane
ring carbon atom bound to the nitrogen atom with the
phosphorus nuclei (3JC–N=C–P 35–37 and 17–18 Hz for
Е- and Z-isomers, respectively), that is in accordance
with the literature data [17]. We found that all the
prepared imidoyl phosphonates VIIIa–VIIId existed
predo-minantly in the Е-configuration [(E : Z ≈ (8–
10) : 1] at room temperature, the N-cyclopropyl group
being trans-located with respect to more bulky
phosphonyl group. Noteworthily, the recently
synthesized N-cyclopropyl-substituted trifluoroacet-
imidoyl phos-phonates exist predominantly in the more
hindered Z-configuration [11]. Likely, thermodynamic
preference towards E- or Z-configuration is determined
by both steric and electronic effects of the substituents.
The most convenient route to the target imidoyl
phosphonates is the reaction of the corresponding
imidoyl chlorides with trialkyl phosphites. The first
representatives of previously unknown benzimidoyl
chlorides VII with cyclopropyl substituent at the
nitrogen atom were prepared following Scheme 2.
N-Cyclopropyl-substituted amides VI were
prepared via acylation of the corresponding cyclo-
propylamines IV with fluorinated benzoic acids
chlorides. Amides IV were converted into imidoyl
chlorides VII with high yield upon heating with
thionyl chloride; the products were liqiuds stable in
anhydrous atmosphere that could be distilled in vacuum.
Heating of imidoyl chlorides VII with triethyl
phosphite led to previously unknown benzimidoyl
phosphonates VIII containing cyclopropyl fragment at
the nitrogen atom. Imidoyl phosphonates VIIIa–VIIId
were colorless or lightly colored liquids that could be
distilled in high vacuum; they were stable in inert
anhydrous atmosphere but were readily hydrolyzed
with moisture. Spectral data of the С-phosphorylated
imines confirmed their suggested structures. Signals of
phosphorus nuclei at the imine carbon atom were
found at 2.6–6.7 ppm, a region typical of benzimidoyl
phosphonates [12, 13]. One of the most informative
signals was that of imine carbon in the 13С NMR
spectrum (δС 162–163 ppm with high spin-spin
1
coupling constant JCP 249–251 Hz) confirming the
Electronic structure of N-cyclopropyl-sub-
stituted imidoyl chloride and imidoyl phosphonate
groups. Taking advantage of fluorine nuclei sensitivity
to the electronic influence of substituents, we have
estimated the electronic effects of N-cyclopropyl-
presence of the P–C=N fragment.
Z/E-Isomerism of N-cyclopropyl-substituted benz-
imidoyl phosphonates. Earlier we have demonstrated
that some imidoyl phosphonates exist in the form of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

420
ONYS’KO et al.
Chemical shifts of fluorine-substituted benzenes XC6H4F and σ-constants of N-substituted imidoyl chloride (nos. 1 and 2)
and imidoyl phosphonate (nos. 3–6) series
δF(XC6H4F)
Run no.
X
σI
σR
0.13
σp
3-F
4-F
1
2
0
3.92
0.09
0.15
0.22
0.30
N CCl−
F3C
0.46
1.35
4.84
1.60
0.15
N CCl−
3
0.275
0.008
0.28
N
P(O)(OEt)2
P(O)(OEt)2
4
5
–0.19
3.10
0.78
2.12
0.06
0.52
0.03
0.09
0.49
N
–0.03
F3C
N
P(O)(OEt)2
6
2.39
0.24
0.42
–0.07
0.35
N
P(O)(OEt)2
F3C
substituted imidoyl chloride and imidoyl phosphonyl
groups for the first time. Having measured the
chemical shifts of fluorine nuclei of imidoyl chlorides
VIIa–VIId and imidoyl phosphonates VIIIa–VIIId in
CDCl3 relative to the fluorobenzene internal reference
and using the Taft relations [(1) and (2)] [18], we
determined inductive and resonance σ-constants of N-
cyclopropyl-substituted imidoyl chloride and imidoyl
phosphonyl moieties.
form for the imidoyl phosphonates VIIIa–VIIId) were
significantly stronger than those of the corresponding
Z-group (cf. nos. 3 and 4; 5 and 6). In accordance to
the data shown in the table, imidoyl phosphonates VIII
were less prone to addition of nucleophilic agents as
compared to the similar N-aryl-, N-sulfonyl-, and N-
phosphonylimidoyl phosphonates.
We have earlier demonstrated that the imidoyl
phosphonates containing α-hydrogen in the N-alkyl
substituent turned to undergo the 1,3-proton shift in the
C=N–C triad to form alkylidenamino phosphonates [2,
19]. On the contrary, the imidoyl phosphonates
containing cyclopropyl (VIIIa, VIIIb) or trifluoro-
methylcyclopropyl (VIIIc, VIIId) group at the
nitrogen atom did not exhibit the prototropic iso-
merization even in the presence of nitrogen bases
(Et3N, 80°C or Et3N–DBU, 80°C).
σI = (δmF + 0.6)/7.1,
σR = (δpF – δmF)/29.5.
(1)
(2)
Analysis of the results (see table) revealed that
imidoyl chloride (nos. 1 and 2) as well as imidoyl
phosphonate (nos. 3–6) groups with cyclopropyl
substituent at the nitrogen atom possessed electron-
accepting properties, the imidoylphosphonate groups
being the stronger acceptors. Introduction of trifluoro-
methyl group at the cyclopropane ring significantly
enhanced the accepting properties of the imidoyl group
(cf. nos. 3 and 5; 4 and 6). Noteworthy, the σ-constant
depended on the geometry configuration: the accepting
properties of Е-imidoyl phosphonate group (the major
EXPRIMENTAL
1Н, 19F, 31Р, and 13C spectra were recorded using a
Varian VXR-300 spectrometer at 299.95, 282.20,
121.42, and 75.429 MHz, respectively. The chemical
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

421
N-(R-CYCLOPROPYL)FLUOROBENZIMIDOYL PHOSPHONATES
shifts are reported with respect to the internal [TMS
(1Н and 13C), CFCl3 or PhF (19F)] or external [85%
Н3РО4 (31Р)] references. All the reactions were
performed in anhydrous media under argon atmosphere.
CHH), 1.84 m (1H, CHCF3), 3.23 m (1H, CHN), 6.50
br.s (1H, NH), 7.21 m (1H, Ar), 7.39 m (1H, Ar), 7.48
m (2H, Ar). 19F NMR spectrum (CDCl3), δF, ppm:
–66.85 d (3F, CF3, 3JFH 6.0 Hz), –111.93 m (1F, ArF).
N-(R-Cyclopropyl)benzimidoyl chlorides (VII).
A mixture of the corresponding amide VI (30 mmol)
and thionyl chloride (36 mmol) was heated at 100°C
until the gas evolution ceased (≈2 h) and distilled in
vacuum.
N-(Cyclopropyl)fluorobenzamides (VIa, VIc). A
solution of 45.4 mmol of the corresponding
fluorobenzoic acid chloride Va or Vb in 20 mL of
anhydrous dichloromethane was added dropwise upon
stirring to a solution of 45.4 mmol of cyclopropyl-
amine IVa and 49.5 mmol of triethylamine in 100 mL
of anhydrous dichloromethane at 0°C. The mixture
was stirred during 12 h at room temperature, washed
with aqueous NaHCO3 (2 × 50 mL), water (3 ×
50 mL), brine (50 mL), and dried over Na2SO4. After
the solvent removal, the residue was crystallized from
the ethyl acetate – hexane 10 : 1 mixture.
N-(Cyclopropyl)-4-fluorobenzimidoyl chloride
1
(VIIa). Yield 95.6%, bp 52–54°C (0.12 mmHg). H
NMR spectrum (CDCl3), δ, ppm: 1.01 m (4H, CH2),
3.47 m (1H, CHN), 7.05 m (2H, Ar), 7.92 m (2H, Ar).
13C NMR spectrum (CDCl3), δС, ppm: 8.86 (CH2),
2
35.31 (CHN), 114.84 d (С3Ar, С5Ar, JCF 22.0 Hz)
3
4
130.20 d (С2Ar, С6Ar, JCF 9.0 Hz), 131.68 d (С1Ar, JCF
3.0 Hz), 139.23 (C=N), 162.00 d (С4Ar, 1JCF 252.0 Hz).
19F NMR spectrum (CDCl3): δF –110.34 ppm.
N-Cyclopropyl-4-fluorobenzamide (VIa). Yield
67%. 1H NMR spectrum (CDCl3), δ, ppm: 0.62 m (2H,
CH2), 0.87 m (2H, CH2), 2.88 m (1H, NСН), 6.37 br.s
(1H, NH), 7.08 m (2H, Ar), 7.75 m (2H, Ar).
N-[(trans-2-Trifluoromethyl)cyclopropyl]-4-fluoro-
benzimidoyl chloride (VIIb). Yield 87%, bp 56°C
1
(0.14 mmHg). H NMR spectrum (CDCl3), δ, ppm:
N-Cyclopropyl-3-fluorobenzamide (VIc). Yield
67%. 1H NMR spectrum (CDCl3), δ, ppm: 0.63 m (2H,
CH2), 0.88 m (2H, CH2), 2.90 m (1H, NСН), 6.29 br.s
(1H, NH), 7.19 m (1H, Ar), 7.39 m (1H, Ar), 7.47 m
(2H, Ar). 19F NMR spectrum (CDCl3): δF –112.32 ppm.
1.41 m (1H, CHH), 1.46 m (1H, CHH), 2.12 m (1H,
CHCF3), 3.80 m (1H, CHN), 7.08 m (2H, Ar), 7.95 m
(2H, Ar). 13C NMR spectrum (CDCl3), δC, ppm: 11.41
3
2
q (CH2, JCF 2.0 Hz), 23.04 q (CHCF3, JCF 37.0 Hz),
37.84 q (CHN, JCF 3.0 Hz), 115.02 d (С3Ar, С5Ar, JCF
3
2
1
N-[(trans-2-Trifluoromethyl)cyclopropyl]fluoro-
benzamides (VIb, VId). A solution of the cor-
responding fluorobenzoic acid chloride (15.4 mmol) in
10 mL of anhydrous dichloromethane was added
dropwise at 0°C upon stirring to a solution of trans-2-
(trifluoromethyl)cyclopropylammonium chloride
(15.4 mmol) and triethylamine (33.9 mmol) in 50 mL
of anhydrous dichloromethane. The reaction mixture
was stirred at room temperature overnight, washed
with aqueous solution of NaHCO3 (2 × 25 mL), water
(3 × 25 mL), brine (25 mL), and dried over Na2SO4.
After the solvent removal, the residue was crystallized
from the ethyl acetate – hexane 10 : 1 mixture.
22.0 Hz), 125.02 q (CF3, JCF 271.0 Hz), 130.44 d
(С2Ar, С6Ar, JCF 8.0 Hz), 131.10 d (С1Ar, JCF 3.0 Hz),
3
4
142.97 (C=N), 164.40 d (С4Ar, JCF 253.0 Hz). 19F
1
NMR spectrum (CDCl3), δF, ppm: –66.46 d (3F, CF3,
3JFH 6.0 Hz), –108.76 m (1F, ArF). Found, %: C 49.50;
H 3.09; Cl 13.43; N 5.31. C11H8ClF4N. Calculated, %:
C 49.74; H 3.04; Cl 13.35; N 5.27.
N-(Cyclopropyl)-3-fluorobenzimidoyl chloride
1
(VIIc). Yield 95%, bp 51–52°C (0.12 mmHg). H
NMR spectrum (CDCl3), δ, ppm: 1.03 m (2H, CH2),
1.04 m (2H, CH2), 3.49 m (1H, CHN), 7.10 m (1H,
Ar), 7.31 m (1H, Ar), 7.63 m (1H, Ar), 7.72 m (1H,
Ar). 13C NMR spectrum (CDCl3), δC, ppm: 9.11 (CH2),
35.42 (=NCH), 115.00 d (С2Ar, 2JCF 24.0 Hz), 117.30 d
N-[(trans-2-Trifluoromethyl)cyclopropyl]-4-fluoro-
1
2
4
(С4Ar, JCF 21.0 Hz), 123.74 d (С6Ar, JCF 3.0 Hz),
benzamide (VIb). Yield 73%. H NMR spectrum
129.25 d (С5Ar, JCF 8.0 Hz), 137.76 d (С1Ar, JCF 8.0
Hz), 138.82 (C=N), 162.17 d (С3Ar, 1JCF 246.0 Hz). 19F
NMR spectrum (CDCl3): δF 113.6 ppm. Found, %: C
60.53; H 4.61; Cl 18.28; N 7.21. C10H9ClFN. Cal-
culated, %: C 60.77; H 4.59; Cl 17.94; N 7.09.
3
2
(CDCl3), δ, ppm: 1.18 m (1H, CHН), 1.36 m (1H,
CHН), 1.83 m (1H, CHCF3), 3.21 m (1H, CHN), 6.45
br.s (1H, NH), 7.10 m (2H, Ar), 7.76 m (2H, Ar). 19F
NMR spectrum (CDCl3), δF, ppm: –66.82 d (3F, CF3,
3JFH 6.0 Hz), –107.67 m (1F, ArF).
N-[(trans-2-Trifluoromethyl)cyclopropyl]-3-fluoro-
benzimidoyl chloride (VIId). Yield 93%, bp 57°C
(0.14 mmHg). H NMR spectrum (CDCl3), δ, ppm:
N-[(trans-2-Trifluoromethyl)cyclopropyl]-3-fluoro-
benzamide (VId). Yield 72%. H NMR spectrum
(CDCl3), δ, ppm: 1.19 m (1H, CHH), 1.37 m (1H,
1
1
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422
ONYS’KO et al.
1.44 m (1H, CHH), 1.49 m (1H, CHH, cyclopropyl),
2.14 m (1H, CHCF3), 3.82 m (1H, CHN), 7.17 m (1H,
Ar), 7.37 m (1H, Ar), 7.65 m (1H, Ar), 7.74 m (1H,
Ar). 13C NMR spectrum (CDCl3), δC, ppm: 11.56 q
m (2H, Ar3,5), 7.40 m (2H, Ar2,6). 13C NMR spectrum
(CDCl3), δС, ppm: 12.99 (NCHCH2), 15.76 d (CH3,
3JCP 6.0 Hz), 24.43 q (CHCF3, 2JCF 37.0 Hz), 38.55 d.d
3
3
2
(=NCH, JCP 36.0, JCF 2.0 Hz), 62.95 d (OCH2, JCP
3
2
(CH2, JCF 2.0 Hz), 23.22 q (CHCF3, JCF 37.0 Hz),
7.0 Hz), 63.02 d (OCH2, 2JCP 6.0 Hz), 115.54 d (C3,5
,
Ar
3
2
1
37.90 q (CHN, JCF 3.0 Hz), 115.18 d (С2Ar, JCF
2JCF 22.0 Hz), 124.86 q (CF3, JCF 271.0 Hz), 129.40
24.0 Hz), 118.08 d (С4Ar, 2JCF 22.0 Hz), 124.98 q (CF3,
d.d (C2,6Ar, JCF 8.0, JCP 4.0 Hz), 162.82 d (C4Ar, JCF
3
3
1
1JCF 270.0 Hz), 123.96 d (С6Ar, JCF 3.0 Hz), 129.44 d
251.0 Hz), 167.32 d (C=N, JCP 223.0 Hz); Z-isomer
4
1
(С5Ar, 3JCF4 8.0 Hz), 137.06 d (С1Ar, 3JCF 8.0 Hz), 142.83
(selected signals), 13.31 (NCHCH2), 15.64 d (CH3,
d (C=N, JCF 3.0 Hz), 162.16 d (С3Ar, JCF 247.0 Hz).
3JCP 6.0 Hz), 39.22 d.d (=NCH, 3JCP 18.0, 3JCF 2.0 Hz),
1
19F NMR spectrum (CDCl3), δF, ppm: –66.48 d (3F,
62.28 d (OCH2, JCP 6.0 Hz), 62.38 d (OCH2, JCP
6.0 Hz), 114.60 d (C3,5Ar, 2JCF 21.0 Hz), 125.14 q (CF3,
1JCF 271.0 Hz). 19F NMR spectrum (CDCl3), δF, ppm:
–66.3 d (3F, CF3, 3JFH 7.0 Hz), –110.50 m (1F, ArF, E-
2
2
3
CF3, JFH 6.0 Hz), –113.14 m (1F, ArF). Found, %: C
49.52; H 3.06; Cl 13.45; N 5.29. C11H8ClF4N.
Calculated, %: C 49.74; H 3.04; Cl 13.35; N 5.27.
3
isomer); –65.94 d (3F, CF3, JFH 4.0 Hz), –111.19 m
(1F, ArF, Z-isomer, E : Z ≈ 8:1). 31P NMR spectrum
(CDCl3), δP, ppm: 6.62 (E-isomer), 2.68 (Z-isomer,
E : Z ≈ 8 : 1). Found, %: C 48.98; H 4.89; N 3.73.
C15H18F4NO3P. Calculated, %: C 49.05; H 4.94; N 3.81.
N-(R-Cyclopropyl)benzimidoyl
phosphonates
(VІII). A mixture of the corresponding imidoyl
chloride VI (25.3 mmol) and triethyl phosphite
(30.4 mmol) was heated during 18 h at 135°C. The
reaction course was monitored with 31P and 19F NMR
spectroscopy. The target imidoyl phosphonates VІIIa–
VІIId were isolated via vacuum distillation.
O,O-Diethyl-N-(cyclopropyl)-3-fluorobenzimidoyl
phosphonate (VIIIc). Yield 83%, bp 110–111°C
1
(0.12 mmHg). H NMR spectrum (CDCl3), δ, ppm:
O,O-Diethyl-N-(cyclopropyl)-4-fluorobenzimidoyl
phosphonate (VIIIa). Yield 84.5%, bp 124°C
0.97 m (2H, NCHCH2), 1.14 m (2H, NCHCH2), 1.28 t
3
(6H, CH3, JHP 7.2 Hz), 3.01 m (1H, =NCH), 4.14 m
1
(0.12 mmHg). H NMR spectrum (CDCl3), δ, ppm:
(4H, OCH2), 7.12 m (2H, Ar), 7.19 m (1H, Ar), 7.42 m
(1H, Ar). 19F NMR spectrum (CDCl3), δF, ppm:
–111.25 (E-isomer), –113.79 (Z-isomer, Е : Z ≈ 10 : 1).
31P NMR spectrum (CDCl3), δP, ppm: 7.75 (E-isomer),
3.72 (Z-isomer, E : Z ≈ 10 : 1). Found, %: C 56.12; H
6.38; N 4.63. C14H19FNO3P. Calculated, %: C 56.19; H
6.40; N 4.68.
0.96 m (2H, NCHCН2), 1.12 m (2H, NCHCН2), 1.27 t
3
(6H, CH3, JHH 7.1 Hz), 3.02 m (1H, CHN), 4.14 m
3
(4H, OCH2), 7.13 t (2H, Ar3,5, JHF 8.5 Hz), 7.43 m
(2H, Ar2,6). 13C NMR spectrum (CDCl3), δС, ppm: Е-
3
isomer, 10.81 (NCHCH2), 15.82 d (CH3, JCP 6.0 Hz),
3
2
36.38 d (CHN, JCP 35.0 Hz), 62.72 d (OCH2, JCP
7.0 Hz), 115.22 d (C3,5Ar, JCF 22.0 Hz), 129.54 d
2
(C2,6Ar, JCF 8.0 Hz), 129.56 d (C1Ar, JCP 8.0 Hz),
3
2
O,O-Diethyl-N-[(trans-2-trifluoromethyl)cyclo-
1
1
162.50 d (C1Ar, JCF 250.0 Hz), 163.18 d (C=N, JCP
propyl]-3-fluorobenzimidoyl phosphonate (VIIId).
1
Yield 85%, bp 106°C (0.12 mmHg). H NMR spec-
225.0 Hz); Z-isomer (selected signals), 11.42 s
3
trum (CDCl3), δ, ppm: 1.28 t (6H, CH3), 1.38 m (1H,
NCHCHH), 1.54 m (1H, NCHCHH), 2.22 m (1H,
CHCF3), 3.28 m (1H, =NCH), 4.15 m (4H, OCH2),
7.14 m (3H, Ar), 7.45 m (1H, Ar). 13C NMR spectrum
(CDCl3), δС, ppm: 13.12 (NCHCH2), 15.84 d (CH3,
3JCP 6.0 Hz), 24.61 q (CHCF3, 2JCF 37.0 Hz), 38.73 d.q
(NCHCH2), 37.19 d (CHN, JCP 17.0 Hz), 61.96 d
2
2
(OCH2, JCP 6.0 Hz), 114.46 d (C3,5Ar, JCF 12.0 Hz),
129.70 d (C2,6Ar, JCF 4.0 Hz), 129.96 d (C1Ar, JCP
3.0 Hz). 19F NMR spectrum (CDCl3), δF, ppm: –111.25
(E-isomer), –112.02 (Z-isomer, Е : Z ≈ 9 : 1). 31P NMR
spectrum (CDCl3), δP, ppm: 8.09 quintet (3JPH 8.0 Hz,
E-isomer), 4.11 quintet (3JPH 8 Hz, Z-isomer, Е : Z ≈
9 : 1). Found, %: C 55.98; H 6.35; N 4.55. C14H19FNO3P.
Calculated, %: C 56.19; H 6.40; N 4.68.
3
2
3
3
2
(=NCH, JCP 35.0, JCF 3.0 Hz), 63.12 d (OCH2, JCP
6.0 Hz), 63.19 d (OCH2, 2JCP 7.0 Hz), 114.40 d.d (C2
,
Ar
2JCF 23.0, JCP 3.0 Hz), 116.46 d (C4Ar, JCF 22.0 Hz),
122.96 d.d (C6Ar, 3JCP 4.0, 4JCF 1.8 Hz), 124.83 q (CF3,
1JCF 271.0 Hz), 130.24 d (C5Ar, 3JCF 8.0 Hz), 134.98 d.d
3
2
O,O-Diethyl-N-[(trans-2-тtrifluoromethyl)cyclo-
(C1Ar, JCP 30.0, JCF 7.0 Hz), 162.25 d (C3Ar, JCF
2
3
1
propyl]-4-fluorobenzimidoyl phosphonate (VIIIb).
1
249.0 Hz), 166.92 d (C=N, JCP 223.0 Hz). 19F NMR
1
Yield 82.3%, bp 103–104°C (0.12 mmHg). H NMR
3
spectrum (CDCl3), δ, ppm: 1.27 m (6H, CH3) 1.37 m
(1H, NCHCHH), 1.54 m (1H, NCHCHH), 2.22 m (1H,
CHCF3), 3.30 m (1H, CHN), 4.14 m (4H, OCH2), 7.17
spectrum (CDCl3), δF, ppm: –66.18 d (3F, CF3, JFH
8.0 Hz), –114.44 m (1F, ArF, E-isomer); –65.98 d (3F,
CF3, 3JFH 6.0 Hz), –113.34 m (1F, ArF, Z-isomer, E : Z ≈
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

423
N-(R-CYCLOPROPYL)FLUOROBENZIMIDOYL PHOSPHONATES
10 : 1). 31P NMR spectrum (CDCl3), δP, ppm: 6.66 (E-
isomer), 2.64 (Z-isomer, E : Z ≈ 10 : 1). Found, %: C
48.71; H 4.91; N 3.75. C15H18F4NO3P. Calculated, %:
C 49.05; H 4.94; N 3.81.
10.1134/S1070428011050010.
11. Onys’ko, P.P., Klukovsky, D.V., Bezdudny, A.V.,
Pirozhenko, V.V., Pustovit, Y.M., and Synytsya, A.D.,
Phosphorus, Sulfur, Silicon, Relat. Elem., 2014,
vol. 189, nos. 7–8, p. 1094. DOI: 10.1080/
10426507.2014.905576.
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