Sigmatropic isomerizations in azaallyl systems: XXI. Alkanimidoylphosphonates and their prototropic and phosphorotropic isomers

Article abstract of DOI:10.1007/s11176-005-0110-8

Synthetic procedures for alkanimidoylphosphoryl derivatives with α-hydrogen atoms in the N-alkyl radical are developed. Data on the effect of substituents at the carbon and phosphorus atoms on the facility of prototropic transitions in the C=N-C triad are

Full text of DOI:10.1007/s11176-005-0110-8

Russian Journal of General Chemistry, Vol. 74, No. 12, 2004, pp. 1868 1878. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004,
pp. 1981 1991.
Original Russian Text Copyright
2004 by Onys’ko, Kim, Kiseleva, Sinitsa.
Sigmatropic Isomerizations in Azaallyl Systems:
XXI.1 Alkanimidoylphosphonates and Their Prototropic
and Phosphorotropic Isomers
P. P. Onys’ko, T. V. Kim, E. I. Kiseleva, and A. D. Sinitsa
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Ukraine, Kiev
Received March 27, 2003
Abstract Synthetic procedures for alkanimidoylphosphoryl derivatives with -hydrogen atoms in the
N-alkyl radical are developed. Data on the effect of substituents at the carbon and phosphorus atoms on the
facility of prototropic transitions in the C=N C triad are summarized. The most facile proton transfer occurs
in the N-benzyl derivatives, and the prototropic isomer is the more stable, the stronger the electron-acceptor
power of the substituent at the sp3-carbon atom of the azaallyl triad. The proton transfer in N-( -phenethyl)-
trifluoroacetimidoylphosphonates proceeds selectively, which allows preparation of enantiomerically enriched
derivatives of -aminotrifluoroethylphosphonic acid. A specific effect of substituents at the phosphorus atom
on the prototropism attendant on phosphorylation of imidoyl chlorides is demonstrated.
The methylene azomethine system is one of the
least labile prototropic triads. An electron-acceptor
phosphorus-containing group at the sp2-carbon atom
of the C=N CH triad much increases the lability of
the proton and thus renders such compounds labile
prototropic systems [2]. Proton transfer in phospho-
rylated azaallyl derivatives is synthetically attractive,
providing a way to converting imidoylphosphonic to
biologically important -aminophosphoryl compounds
[3, 4]. The 1,3-phosphorotropic isomerization we
discovered in the C=N CH triad [5, 6] permits to
perform interconversions of different -aminophos-
phoryl derivatives.
as the effect of substituents on the phosphorus atom
on the prototropism attendant on phosphorylation of
imidoyl chlorides.
As one of the synthetic approaches to imidoylphos-
phoryl compounds, we for the first time used the aza-
Wittig reaction with acetylphosphonate I as the
carbonyl component. It was found that imidoylphos-
phonate III formed by the reaction of oxophosphonate
I with phosphazo compound II undergoes irreversible
isomerization to -phosphorylated benzalimine IV
under the reaction conditions. The preference for the
imine imine isomerization over the imine enamine
rearrangement III V (Scheme 1) is assignable to the
possibility of effective conjugation of the C=N bond
with the phenyl ring in N-benzylidene structure IV,
which makes this structure favorable [2, 7].
In the present work we considered the effect of
alkyl groups at the sp2- and sp3-carbon atoms of a
phosphorylated azaallyl triad on the facility of 1,3-
prototropic and phosphorotropic transitions, as well
Scheme 1.
O=P(OEt)2
N
H
H3C
Ph
Ph
O
O=P(OEt)2
N
1,3-H
IV
H3C
+ Ph3P=N
P(OEt)2
Ph
Ph
Ph3PO
O=P(OEt)2
H3C
O
I
II
III
N
H
H
H
V
1
For communication XX, see [1].
1070-3632/04/7412-1868 2004 MAIK Nauka/Interperiodica

SIGMATROPIC ISOMERIZATIONS IN AZAALLYL SYSTEMS: XXI.
1869
The mild conditions of the III IV isomerization
(room temperature) are probably explained by the
catalytic effect of phosphazo compound II as a base.
Evidence for this assumption comes from the fact that
P-imidoylphosphazo compound VIIa undergoes
spontaneous isomerization already during distillation
(Scheme 2), whereas phosphonates VIIb VIId
lacking the basic phosphazo group are distilled un-
changed. In the latter case, for 1,3-H shift to occur
requires more rigid conditions (160 170 C) [6 9].
The most convenient synthetic approach to imidoyl-
phosphonates VII is reaction of a stable imidoyl
chloride VI containing no -hydrogen atoms in the
substituent at the imidoyl carbon atom with a P(III)
derivative [6 9]. Isomeric -phosphorylated imines
VIIIb and VIIIe were obtained independently by
condensation of aminophosphoryl compounds IX with
benzaldehyde. It is important to note that compounds
VII and VIII are kinetically stable and do not inter-
convert under usual conditions.
Scheme 2.
(EtO)2PNHPh, Et3N
or
X=PR2
X=PR2
Cl
R2POAlk (XI)
1,3-H
N
Ph
N
Ph
N
Ph
t-Bu
t-Bu
t-Bu
VI
VIIa VIIe
VIIIa VIIIe
O=PR2
NH2 + PhCHO
IXa, IXb
VII, VIII, X = PhN (a), O (b e); R = EtO (a, b), i-PrO (c), Me3SiO (d), Ph (e); IX, R = EtO (a), Ph (b).
H2O
t-Bu
X
When heated (160 180 C), compounds VIII un-
dergo phosphorotropic rather than prototropic isome-
rization in the C=N C triad [5, 6, 9]. At the same
time, to effect irreversible 1,3-H shift in imidoyl
derivatives VII requires heating to 140 160 C or base
isomerization in compounds XIII proceeds either
upon their synthesis from imidoyl chloride XII (R =
Ph) in the course of distillation or even at room
temperature (slowly) [6, 11]. The strongly electron-
acceptor phosphonium group at the imidoyl carbon
atom favors proton transfer [2, 7, 12]. When R=Ph
and Alk, quasiphosphonium intermediates are more
stable, and their lifetime is sufficient for A to iso-
merize into B (Scheme 3) [6, 13].
catalysis. Replacement of the tert-butyl group (
I
0.02) at the imidoyl carbon atom by the electron-
acceptor trifluoromethyl group ( 0.43 [10]) facili-
I
tates 1,3-H shift considerably. Spontaneous prototropic
Scheme 3.
O
+ Cl
R2P OAlk
R2P
Cl
CF3
N
Ph
Ph
N
CF3
Ph
N
Ph + R2POAlk
AlkCl
CF3
XII
XI
A
XIII
R = Ph 1,3-H
O
+ Cl
R2P OAlk
R2P
N
N
Ph
AlkCl
CF3
CF3
B
XIV
R = MeO, EtO, i-PrO, Me3SiO, Ph, Et.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1870
ONYS’KO et al.
The lability of the proton in N-methyl or N-( -phe-
XV are quite stable compounds and do not undergo
isomerization even on heating. To effect 1,3-H shift in
them requires catalysis with nitrogenous bases
(Scheme 4).
nethyl)imidoylphosphonates is significantly decreased
as compared to their N-benzyl analogs. Unlike easily
isomerized compounds XIII, imidoylphosphonates
Scheme 4.
R
*
R
R
O=P(OAlk)2
O=P(OAlk)2
Cl
B
(AlkO)3P
N
R
N
R
*
N
R
CF3
CF3
CF3
XVa XVd
XVIa XVId
XV, XVI, R = R = H, Alk = Et (a); R = Me, R = Ph, Alk = Me (b), Et (c), i-Pr (d).
In the presence of triethylamine, isomerization of
N-methyltrifluoroacetimidoylphosphonate XVa occurs
even at room temperature, but resulting unstable
methylenimine XVIa undergoes isomerization to give
a mixture of unidentified products. Spectral identifica-
tion of -phosphorylated imine XVIa was carried out
chemical shifts ( 2.1 and 4.37 ppm, respectively).
P
Actually compounds XVb and XVc (
2.2 to
P
4.4 ppm), like other N-alkyl and N-acyltrifluoroacet-
imidoylphosphonates, absorb upfield with respect to
H3PO4 (see [7] and references therein). Note that the
presence of two electron-acceptor groups, phosphoryl
and trifluoromethyl, at the imidoyl carbon atom of
compound XV is a necessary condition for 1,3-H shift.
Hence, replacement of the CF3 group in compounds
by comparison of its spectral characteristics (
P
3
12.3 ppm,
63.4 ppm, d.d, JFH 3JPF 7 Hz) with
F
those of compound XIV. We previously showed [11,
14] that N-( -phenethyl)trifluoroacetimidoylphos-
phonates XVb XVd in the presence of bases (DBU,
Dabco, triethylamine) undergo irreversible 1,3-H shift
to form stable -phosphorylated N-alkylidenetrifluo-
roethylamines XVIb XVId. The isomerization is
accelerated with increasing concentration of the base.
The H-shift rate constant (k) for phosphonate XVc,
XV by phenyl (
0.10 and 0.42, respectively
[10, 17]) prevents prIoton transfer in the C=N C triad
of the corresponding benzimidoylphosphonates [1].
In N-benzyl derivatives III and VII that contain
methyl or tert-butyl groups at the C=N bond, only one
electron-acceptor phosphoryl group is sufficient for
proton transfer to occur (Schemes 1 and 2). This also
holds true for phosphonates XVIII in which the
imidoyl carbon atom is bound with an alkenyl radical.
Here, however, consecutive proton transfer in the aza-
allyl and allyl triads takes place [18] (Scheme 5) to
give phosphorylated azadiene XX. The XVIII XIX
izomerization suggests that the conjugated alkene
azomethine system is less favorable than the benzyl-
idene one. The motive force of the XIX XX iso-
merization may be formation of azadiene XX contain-
ing a benzylidene fragment and a longer conjugation
chain.
5
1
was estimated at 7.5 10
s
([Et3N] = [XVc]0 =
0.42 M, toluene, 90 C). The proton transfer is stereo-
selective and allows preparation of enantiomerically
enriched phosphorus-containing analogs of trifluoro-
alanine [14]. Later analogous results were obtained
by Xiao et al. [15]. Note that the referees [15] mis-
takenly reported a negative rotation angle for
(+)-imine XVIc formed by isomerization of
( )-imidoylphosphonate XVc [14]. For imidoylphos-
phonates XVb and XVc first prepared by us in [11],
Yuan and Zhang [16] gave wrong phosphorus
Scheme 5.
O=P(OR)2
O=P(OR)2
R
O=P(OR)2
Cl
1,3-H
1,3-H
(RO)3P
N
Ph
N
Ph
N
Ph
N
R
XVII
XVIII
XIX
XX
R = Me, Et, i-Pr.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

SIGMATROPIC ISOMERIZATIONS IN AZAALLYL SYSTEMS: XXI.
1871
Comparison of the conditions of the 1,3-H shift in
imidoylphosphonates VIIb, VIIc, and XVIII shows
that the presence of the electron-acceptor alkenyl
(CH2=CMe > t-Bu). The effect of substituents on
phosphorus on prototropism is clearly pronounced in
the reactions of imidoyl chlorides VI and XII with
triethyl phosphite, ethyl diphenylphosphinite, and
diethyl phenylphosphonite (Scheme 6).
substituent ( for CH2=CMe is 0.10 [17]) at the
I
imidoyl carbon atom favors proton transfer
Scheme 6.
Cl
O
+
R R P
R R P OEt
Cl
R
N
Ph
N
Ph
N
Ph + R R POEt
EtCl
R
R
VI, XII XXIa XXIc
C
XXIIa XXIIf
1,3-H
OEt
O
R = t-Bu,
R = EtO,
R = Ph
O=P
Cl
+
Ph
Ph
R R P
H
R R P OEt
N
Ph
N
N
R
Ph
EtCl
R
t-Bu
D
XXIIIa XXIIIf
XXIV
R = t-Bu (VI), CF3 (XII); XXI, R = R = EtO (a), Ph (b); R = EtO, R = Ph (c); XXII, XXIII, R = R = EtO, R = t-Bu
(a), CF3 (b); R = R = Ph, R = t-Bu (c), CF3 (d); R = EtO, R = Ph, R = t-Bu (e), CF3 (f).
The reaction of imidoyl chloride VI with triethyl
phosphite (XXIa) forms imidoylphosphonate XXIIa
which is stable in usual conditions and isomerizes at
high temperature [8, 9]. The reaction with imidoyl
chloride XII gives a mixture of prototropic isomers
XXIIb and XXIIIb, the latter prevailing. In the
the C=N bond (Scheme 5) directly affect facility of
proton transfer in the C=N C triad (CF3 > CH2=CMe
> Ph > t-Bu). As phosphorus groups R R P(O) in
compounds XXII only slightly differ in electronic
nature {the
values of the (EtO)2P(O) and Ph2P(O)
groups are 0.I35 and 0.30, respectively [10]}, it is
evident that the effect of substituents on phosphorus
on prototropism is determined by their effect on the
relative stability and, therefore, lifetime of quasiphos-
phonium salts C: (XXIb > XXIc > XXIa). The high
electon-acceptor capacity of phosphonium groups
favors proton transfer [2, 7, 12]. For this reason, at a
sufficient lifetime of intermediate C the prototropic
course of distillation the XXIIb
XXIIIb isomeriza-
tion completes [11]. The reaction of imidoyl chlorides
VI and XII with phosphinite XXIb results in ex-
clusive formation of prototropic isomers XXIIIc and
XXIIId in both cases [6]. And, finally, phosphonite
XXIc reacts with imidoyl chloride VI to form a mix-
ture of prototropic isomers XXIIe and XXIIIe in a
1.4:1 ratio, and the reaction with trifluoroacetimidoyl
chloride XII provides no other products than imine
XXIIIe. Compounds XXIIe and XXIIIe were not
isolated pure, since the prototropic isomerization
isomerization C
XXIII. A specific feature of phosphinates
XXIIe and XXIIf is the presence of achiral
phosphorus atom. The XXIIe, XXIIf XXIIIe,
XXIIIf or C XXIIIe, XXIIIf isomerizations
D precedes the dealkylation stage
D
XXIIe
XXIIIe that occurs on heating (or distilla-
D
tion) of the mixture of XXIIe and XXIIIe is accom-
panied by transfer of the phosphorus-containing group
to form imine XXIV (cf. [5, 6, 9]).
give rise to one more chiral center, a carbon atom
bound with phosphorus. Compound XXIIIf is formed
as a diastereomeric mixture ( 1.3:1), whereas with
XXIIIf, only one diastereomer is formed. Hence, the
prototropic isomerization attendant on the phospho-
rylation of imidoyl chlorides VI and XII with phosphi-
nite XXIb is diastereoselective. The enhancement of
the diastereoselectivity in passing from XXIIIf to
Hence, the prototropic transformations attendant in
phosphorylation of imidoyl chlorides depends both
on substituents at the imidoyl carbon atom and
in the phosphorus reagent; however, the these
effect significantly differ in nature. Substituents R at
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1872
ONYS’KO et al.
XXIIIe is evidently explained by a stronger steric
demand of the bulky tert-butyl group.
nonequivalence of the doublet proton signals of the
prochiral NCH2 group in the H NMR spectra (see
1
Experimental).
Evidence for the presence of two diastereomers of
XXIIIe comes from the observation of doubled CF3
and phosphorus signals in the 19F and 31P NMR spec-
tra, as well as of CH N proton signals in the 1H NMR
spectra. The asymmetric phosphorus atom in imidoyl-
phosphinate XXIIe is responsible for the magnetic
Prototropic isomers XIV and XVI can be prepared
independently by condensation of aminophosphonate
XXV with the corresponding carbonyl compounds
(Scheme 7).
Scheme 7.
O
O
R
(EtO)2P
(EtO)2P
R
R
N
NH2 +
O
H2O
CF3
R
CF3
XXV
XVIe XVIr
XVI, R = H, R = t-Bu (e), 2-thienyl (f), 2-HO-4-MeOC6H3 (g); R + R = (CH2)4 (h); R = (EtO)2P(O), R = t-Bu (i), Me
(j) [19], Ph (k) [19]; R + R = 1-R3-5-R4-7-R5-2-oxoindolinyl-3-idene [20], where R3 = R5 = H, R4 = H (l), Cl (m), Br
(n), NO2 (o); R3 = H, R4 = R5 = Cl (p); R4 = R5 = H, R3 = PhCH2 (q), 2-FC6H4CH2 (r).
Independently of substituents R and R , prototropic
O=P(OEt)2
isomers XIV and XVIb XVIr are stable compounds
Cl
Ph
Ph
N
N
that do not convert into imidoyl isomers XIII and XV
under heating or nitrogenous base catalysis. This also
relates to compounds XVIl XVIr whose imine carbon
atom is incorporated into the isatine heteroring con-
taining the electron-acceptor C=O group in the
position [20].
N
t-Bu
t-Bu
XXVI
XXVII
XXVIII
also reveals itself in vinylogs of phosphorylated aza-
allyl compounds XXIX (CF3 > Ph), where the
imidoyl carbon atom and migrating proton are inter-
vened by an additional C=C fragment (Scheme 8) [23].
Substituents at the carbon atoms of the C=N C
triad exert a considerable effect both on thermody-
namic preference of the prototropic isomers and their
tendency for 1,3-H shift. Electron-acceptor substi-
tuents facilitate proton transfer, and, other conditions
being equal, an isomer that has the strongest electron-
acceptor substituents at the sp3-carbon atom, is the
most thermodynamically favorable [2, 7, 21]. Hence,
proton transfer in (N-methyltrifluoroacetimidoyl)-
phosphonate in the presence of Et3N takes place at
20 C (Scheme 4), and imidoylphosphonate XXVI
with the weaker electron-acceptor Me2CCl group at
the imidoyl carbon atom is stable under analogous, as
well as more rigid conditions [22]. Contrary to easily
isomerized N-benzimidoylphosphonates VII, N-benzyl-
imine XXVII containing no phosphorus at the imine
carbon atom is insusceptible to proton transfer even
on heating in the presence of nitrogenous bases (DBU,
Dabco), even though N-benzylidene isomer XXVIII
is evidently thermodynamically more favorable.
Scheme 8.
Me
R
R
1,5-H
N
N
(EtO)2P
O
(EtO)2P
O
XXIX
XXX
R = CF3, Ph.
Comparison of Schemes 3, 4, and 9 demonstrates
the effect of substituents in the N-alkyl radical of
imidoylphosphonates on prototropism. Compound
XIII with an N-benzyl group easily isomerizes even
in the absence of bases (Scheme 3). Introduction of
the electron-donor methyl (
0.05) and the electron-
I
acceptor phenyl group ( 0.1) [17] complicates iso-
merization. To effect the XV XVI conversion
requires base catalysis (Scheme 4) [11, 14], and in
The activating effect of electron-acceptor substitu-
ents at the imidoyl carbon atom on proton transfer
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

SIGMATROPIC ISOMERIZATIONS IN AZAALLYL SYSTEMS: XXI.
1873
compound XXXIb (Scheme 9) no proton transfer was
found [24]. Treatment of compound XXXIb with base
does not cause isomerization but leads to dehydroflu-
orination to form azadiene XXXII (Scheme 9) [24].
Benzimidoylphosphonates XXXIc with two electron-
acceptor trifluoromethyl groups at the sp3-carbon
atom are also not prone to proton transfer [1]. It is
evident that the formation of a favorable benzylidene
structure like XIV, where there are optimal conditions
for conjugation of the C=N bond with the aryl radical,
is primarily responsible for the easy isomerization of
N-benzylimidoylphosphonates.
Scheme 9.
Ph
Ph
R
R
O=P(OAlk)2
Cl
F
N
???
(AlkO)3P
N
R
R
N
R = CHF2,
R
R = R = Ph
R
O=P(OEt)2
XXXIa XXXIc
XXXII
R = R = Ph, R = CF3 (a), CHF2 (b); R = Ph, R = R = CF3 (c).
Hence, in terms of the tendency for prototropic
electron-acceptor trifluoromethyl group is com-
paratively stable in usual conditions and can be used
for preparing functional derivatives with a trifluoro-
ethylphosphonic acid fragment. Schemes 7 and 12
demonstrate the possible syntheses of imines, N-acyl-
aminophosphonates, and C-phosphorylated ureas.
transformations the above-described systems can be
arranged in the following series: XIII > XVIII >
VII > XV > XXVI,XXVII, XXXI; XXIIb, XXIId,
XXIIf > XXIIa, XXIIc, XXIIf. Proton transfer in
N-benzylalkanimidoylphosphonates III, VII, XIII,
and XV can be used as a synthetic approach to
-aminoalkylphosphonates and phosphonic acids [1,
20] (Schemes 2 4, 6, 10).
Scheme 12.
O
O
O
(EtO)2P
(EtO)2P
Scheme 10.
Et3N
NH2 + RCOCl
R
N
H
O=P(OH)2
H3O+
CF3
CF3
VIId
VIIId
t-Bu
NH2
XXIV
XXXVIa XXXVIf
XXXIII
O=P(OH)2
XXXVI, R = Ph (a), 4-FC6H4 (b), 2,4-Cl2C6H3 (c), 3,5-
(NO2)2C6H3 (d), 3,4,5-(MeO)3C6H2 (e), 2-thienyl.
O=P(OH)2
XIII
XIV
CF3
NH2
CF3
NH2
XXXIV
O
XXV
O
(EtO)2P
R
Mild hydrolysis of imine VIId leads to compound
XXXV, a rare representative of imidoylphosphonic
acids (Scheme 11).
N
H
N
H
XXIV + RNCX
CF3
XXXVIIa XXXVIIc
Scheme 11.
XXXVII, R = 3,4-Cl2C6H3, X = O (a); R = cyclohexyl,
X = O (b); R = Ph, X = S (c).
OSiMe3
OSiMe3
OH
OH
O=P
t-Bu
O=P
H2O
It is important to note that the synthesis of -amino-
alkylphosphoryl derivatives by means of prototropic
rearrangements is especially attractive for phosphory-
lation of N-benzyl-substituted imidoyl chlorides
(Schemes 2, 3, 5, and 6). In this case, the proton
N CH2Ph
t-Bu
XXXV
N CH2Ph
VIId
Trifluoroethylaminophosphonate XXV with the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1874
ONYS’KO et al.
transfer in the C=N C triad takes place just under
phosphorylation conditions. A specific feature of
phosphorus nucleophiles is the ability of phosphorus
to give derivatives of different coordination. Phos-
phorylation may be accompanied by changes both in
valence and in coordination. It is these circumstances,
specifically relative stability of highly electron-ac-
ceptor intermediates of the Arbuzov reaction, like A
and C (Schemes 3 and 6), that are responsible for the
fact that proton transfer may take place at the stage of
quasiphosphonium intermediates, and the established
regularities of the effect of substituents on the phos-
phorus and carbon atoms on the prototropism in the
C=N C triad allow one to control this process.
doylphosphonate, 0.1 g, and 0.2 ml of triethylamine
were mixed at 20 C, and the mixture was studied by
NMR spectroscopy. After 2.5 h, the signal of starting
phosphonate XVa ( 4.4 ppm) disappeared. Signals of
imine XVIa ( 12.3 ppm), aminophosphonate XXV
P
(
17.5), and unidentified compounds ( 0.15 and
P
P
32.9 ppm) were detected in a 15:2:1:1 ratio. A day
later, the signals of imine XVIa disappeared, and
unidentified signals at P 19.0 and 21.7 ppm appeared.
Treatment of imidoylphosphonate XVa with Dabco
or DBU in benzene at 20 C leads to the similar results:
First phosphonate XVa isomerizes into imine XVIa
and then the latter product converts into unidentified
compounds.
EXPERIMENTAL
( )-2-(Diisopropoxyphosphinoyl)-1,1,1-trifluoro-
4-phenyl-3-azabut-2-ene (XVd) was prepared from
( )-N-( -phenethyl)trifluoroacetimidoyl chloride and
triisopripyl phosphite analogously to [14], yield 60%,
bp 104 105 C (0.05 mm Hg), [ ]D 63.3 (c 10,
The IR spectra were measured on a UR-20 spec-
trometer. The H, 19F, and 31P NMR spectra were
1
measured on a Varian VXR-300 spectrometer at
299.95, 282.20, and 121.42 MHz, respectively. The
chemical shifts were measured against internal TMS
(1H) and CFCl3 (19F) and external 85% phosphoric
acid (31P).
benzene). 31P NMR spectrum (CHCl3),
6.4 ppm.
P
(+)-4-(Diisopropoxyphosphinoyl)-5,5,5-trifluoro-
2-phenyl-3-azabut-2-ene (XVId). To a solution of
1.3 g of imidoylphosphonate XVd in 10 ml of toluene,
0.12 g of Dabco was added, and the resulting mixture
was heated at 100 C for 3 h. Removal of the solvent
and distillation gave 65% of enantiomerically enriched
phosphonate XVId, bp 108 109 C (0.06 mm Hg),
[ ]D +31.2 (c 5.5, benzene). 1H NMR spectrum
(CDCl3), , ppm: 1.30, 1.32, 1.35 all d (12H, CH3CH,
3-(Diethoxyphosphinoyl)-1-phenyl-2-azabut-1-
ene (IV). To a solution of 6.8 mmol of phosphazo
compound II in 15 ml of benzene, a solution of
6.8 mmol of acetylphosphonate I was added dropwise
at 5 C. The reaction mixture was heated to room
temperature and left to stand for 2 h. Benzene was
evaporated, and the residue was extracted with petro-
leum ether (40 60 C, 5 10 ml). The solvent was
evaporated, and the residue was distilled in a vacuum.
Yield 54%, bp 133 134 C (0.07 mm Hg). IR spec-
5
3JHH 6 Hz), 2.39 d (3H, CH3C=, JHP 3 Hz), 4.64 d.q
2
3
(1H, CHP, JHP 17 Hz, JHF 8.5 Hz), 4.70 m (1H)
and 4.81 m (1H), both (OCH3), 7.4 m (3H, Ph),
7.91 m (2H, Ph). 13C NMR spectrum (CDCl3),
,
1
C
trum (CCl4), , cm : 1047 (P O C), 1275 (P=O),
3
ppm: 16.12 s (MeC), 23.53 d (MeCH, JCP 5.7 Hz),
1
1674 (C=N). H NMR spectrum (CDCl3), , ppm:
3
3
23.89 d (MeCH, JCP 5.2 Hz), 24.08 d (MeCH, JPC
1.31 t and 1.33 t (6H, MeCH2), 1.57 d.d (3H, MeCH,
3
4 Hz), 34.32 d (MeCH, JCR 4 Hz), 63.52 d.q (CHP,
3JHP 18 Hz, JHH 7 Hz), 3.88 d.q (1H, CHP, 2JHP 15,
2
2
3
1JCP 155 Hz, JCF 28 Hz), 72.58 d (CHO, JCP 8 Hz),
3JHH 7 Hz), 4.17 m (4H, OCH2), 7.4 m (3H, Ph),
1
3
123.79 q.d (CF3, JCF 279 Hz, JCP 3 Hz), 127.27 and
128.27 s (o- and m-CPh), 130.56 (p-CPh), 139.84 (ipso-
CPh), 171.70 d (C=N, 3JCP 11 Hz). 31P NMR spectrum
(CDCl3), P, ppm: 11.34. Found,%: F 15.57; P 8.86.
C16H23F3NO3P. Calculated,%: F 15.60; P 8.48.
4
7.7 m (2H, Ph), 8.34 d (1H, CH=N, JHP 4.8 Hz). 31P
NMR spectrum (CDCl3):
25.8 ppm. Found, %: N
5.18; P 11.50. C13H20NO3PP. Calculated, %: N 5.20; P
11.50.
(3-Diethoxyphosphinoyl)-4,4,4-trifluoro-2-aza-
but-1-ene (XVa). A solution of 20 mmol of N-methyl-
trifluoroacetimidoyl chloride and 20 mmol of triethyl
phosphite in 4 ml of toluene was heated in a sealed
ampule at 110-120 C for 4 h and then distilled in a
vacuum. Yield 55%, bp 94 97 C (12 mm Hg), nD20
5-(Diethoxyphosphinoyl)-2,2-dimethyl-6,6,6-tri-
fluoro4-azahex-3-ene (XVIe). A mixture of 20 mmol
of aminophosphonate XXV and 22 mmol of pivalal-
dehyde was heated at 65 70 C for 5 h, and the pro-
duct was distilled in a vacuum. Yield 58%, bp 54
1
56 C (0.05 mm Hg), nD20 1.4076. H NMR spectrum
1.4004,
4.4 ppm {published data [25]: bp 95
P
(CCl4), , ppm: 1.43 s (9H, t-Bu), 1.67 t (6H, MeCH2),
3.67 4.80 m (5H, OCH2+CHP), 7.98 d (1H, CH=N,
4JHP 4.2 Hz). Found, %: N 4.88; P 10.14. C11H21F3
NO3P. Calculated, %: N 4.62; P 10.21.
97 C (12 mm), n2D0 1.4005,
5.3 ppm}.
P
Isomerization of N-methyltrifluoroacetimidoyl-
phosphonate (XVa) under the action of bases. Imi-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

SIGMATROPIC ISOMERIZATIONS IN AZAALLYL SYSTEMS: XXI.
1875
3-(Diethoxyphosphinoyl)-4,4,4-trifluoro-1-(2-
thienyl)-2-azabut-1-ene (XVIf). Equimolar mixture
of aminophosphonate XXV and 2-thienylcarbaldehyde
was kept for 1 day at room temperature in the pre-
sence of a catalytic amount of p-toluenesulfonic acid.
The product was distilled in a vacuum. Yield 36%, bp
7.9 m (10H, Ph), 8.30 d (0.43 H, CH=N, 4JHP 3.8 Hz),
4
8.40 d (0.57 H, CH=N, JHP 3.8 Hz). 31P NMR spec-
trum (acetone-d6), P. ppm:
31.61,
34.31,
:
1
2
1 2
1.3:1. 19F NMR spectrum (acetone-d6), F, ppm:
69.55,
69.39. Found, %: F 16.49; P 8.671.
2
C17H17F3NO2P. Calculated, %: F 16.04; P 8.72.
127 128 C (0.3 mm Hg), n2D0 1.4980. H NMR spec-
1
trum (CDCl3), , ppm: 1.3 m (6H, MeCH2), 4.1 m
Reaction of imidoyl chloride VI with diethyl
phenylphosphonite (XXIc). Equimolar mixture of
imidoyl chloride VI and diethyl phenylphosphonite
XXIc was heated in an inert atmosphere at 60 110 C
until gas evolution was no longer observed (2 h).
Vacuum distillation gave a fraction with bp 168
175 C (0.1 mm Hg), yield 69%, colorless viscous
(5H, OCH2 + CHP), 7.0 m (2H, thienyl), 8.47 d (1H,
4
CH=N, JHP 3.8 Hz). 31P NMR spectrum (CHCl3),
,
P
ppm: 12.1. 19F NMR spectrum (CDCl3), F, ppm:
68.3. Found, %: N 4.35; P 9.46; S 9.76. C11H15F3
NO3PS. Calculated,%: N 4.25; P 9.41; S 9.74.
3-(Diethoxyphosphinoyl)-1-(2-hydroxy-4-meth-
oxyphenyl)-4,4,4-trifluoro-2-azabut-1-ene (XVIg).
A solution of equimolar amounts of aminophosphona-
te XXV and 2-hydroxy-4-methoxybenzaldehyde in
benzene was refluxed with a Dean Stark trap for 10 h.
The solvent was evaporated, and the residue was kept
in an oil pump vacuum at 20 C. Yield of the target
1
liquid. According to the H NMR spectrum (acetone-
d6 CCl4), it is a mixture of prototropic isomers XXIIe
and XXIIIe and unidentified admixtures. Imidoyl-
phosphonate XXIIe, 1H NMR spectrum, , ppm:
4
1.04 s (9H, Me3C), 4.58 d (1H, JHP 3.5 Hz) and
4
4.67 d (1H, JHP 4.0 Hz) (NCH4AHB). Imine XXIIId,
1H NMR spectrum, , ppm: 1.11 s (9H, Me3C), 3.47
1
product 75%. H NMR spectrum (CDCl3), , ppm:
2
4
d (1H, CHP, JHP 15 Hz), 8.12 d (1H, CH=N, JHP
4.5 Hz). The Ph and OCH2 signals of isomers XXIIe
and XXIIIe overlap. Upon heating of the mixture
(140 160 C), CHP proton signals of two diastereo-
mers of phosphorotropic isomer XXIV appear, ppm:
1.33 t and 1.37 t (6H, MeCH2), 3.79 s (3H, MeO),
4.1 4.3 m (5H, CH2O + CHP), 6.82 d (1H, 3-HAr,
3
4JHH 3.3 Hz), 6.93 d (1H, 6-HAr, JHH 9 Hz),
7.02 d.d (1H, 5-HAr, 3JHH 9, 4JHH 3.3 Hz), 8.45 d (1H,
4
CH+N, JHP 3.6 Hz), 11.6 br (NH). 31P NMR spec-
trum (CDCl3), P, ppm: 11.9. 19F NMR spectrum
4.86 d (2JHP 16 Hz);
4.94 d (2JHP 17 Hz).
2
1
3
(CDCl3), F, ppm: 89.0, JFH 3JFP 7.5 Hz. Found,
(1-Amino-2,2-dimetylpropyl)phosphonic acid
%: F 15.61; P 8.05. C14H19F3NO5P. Calculated,
%: F 15.43; P 8.39.
(XXXIII). A mixture of 1.5 g N-(1-chloro-2,2-di-
methylpropylidene)benzylamine and 2.4 g of tris(tri-
methylsilyl) phosphite was heated for 1 h at 160 C
and distilled in a vacuum to obtain 1.87 g (66%) of
imidoylphosphonate VIId [9], bp 109 111 C
Diethyl 1-(cyclopentylideneamino)-2,2,2-triflu-
oroethylphosphonate (XVIh) was prepared similarly
1
to compound XVIg. Yield 70%. H NMR spectrum
(CDCl3), , ppm: 1.3 t (6H, MeCH2), 1.7 2.7 m (8H,
1
(0.05 mm Hg). H NMR spectrum (CDCl3), , ppm:
cyclopentyl), 4.1 4.4 m (5H, CH2O + CH2P). 31P
0.21 s (18H, Me3Si), 1.27 s (9H, Me3C), 4.92 s (2H,
CH2), 7.3 m (5H, Ph). 31P NMR spectrum (CCl4):
15.67 ppm. Compound VIId was heated for 1 h aPt
180 C. Under these conditions, it isomerized into
NMR spectrum (CDCl3), P, ppm: 14.1. 19F NMR
3
spectrum (CDCl3), F, ppm: 68.8 d.d, JFH
3JFP
8.8 Hz. Found, %: F 18.13; P 10.36. C11H1F3NO3P.
Calculated, %: F 18.92; P 10.28. According to the 19F
and 31P NMR spectra, the product contains about
20 mol% of a compound which is probably the
1
compound VIIId [9]. H NMR spectrum (CDCl3), ,
ppm: 0.15 and 0.19 s (18H, Me3Si), 1.05 s (9H,
2
Me3C), 3.15 d (1H, CHP, JHP 15.0 Hz), 7.2, 7.7 m
enamine isomer of phosphonate XVIh:
13.8 ppm,
P
4
(5H, Ph), 8.12 d (1H, CH=N, JHP 7.8 Hz). 31P NMR
68.5 ppm.
F
2
spectrum (CDCl3), P, ppm: 4.88 d JHP 14.7 Hz, 4JHP
6.0 Hz). Phosphonate VIIId was treated with 12 ml
of 6N HCl and extracted with chloroform (3 5 ml).
The aqueous layer was evaporated, the dry residue
was dissolved in 12 ml of anhydrous ethanol, and
0.33 ml of propylene oxide was added. The precipitate
that formed was filtered off. Yield 0.56 g (72%), mp
1-Phenyl-3-[ethoxy(phenyl)phosphinoyl-4,4,4-
trifluoro-2-azabutene-1 (XXIIIf). An equimolar
mixture of imidoyl chloride XII and diethyl phenyl-
phosphonite XXIc was heated under the inert atmos-
phere until the completion of gas evolution at 70
110 C for 1 h. The resulting mixture was distilled in
a vacuum to give the target product in 48% yield, bp
185 190 C (0.3 mm Hg), crystallizes on handling. H
NMR spectrum (acetone-d6) , ppm: 1.28 1.47 m
(3H, CH3CH2), 3.9 4.5 m (3H, OCH2 + CHP), 7.3
1
259 260 C (from aqueous ethanol). H NMR spec-
1
trum (CF3COOD), P, ppm: 0.93 s (9H, CH3), 3.32 d
2
(1H, CH, JHP 16.0 Hz). 31P NMR spectrum (H2O),
P, ppm: 11.99 d (2JPH 16.0 Hz). Found, %: C 35.88;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

1876
ONYS’KO et al.
H 8.27; N 8.41; P 18.53. C5H14NO3P. Calculated, %:
C 35.93; H 8.46; N 8.38; P 18.53.
and 1.38 t (6H, MeCH2), 4.23 m (4H, OCH2),
3
5.36 m (1H, CHP), 7.08 d (1H, NH, JHH 10 Hz),
7.16 m (2H, Ph). 7,90 m (2H, Ph). 31P NMR spectrum
(1-Amino-2,2,2-trifluoroethyl)phosphonic acid
(XXXIV). A mixture of 2.6 g of N-benzyltrifluoro-
acetimidoyl chloride and 2.1 g of triethyl phosphite
was heated for 3 h at 120 C and then distilled in a
vacuum to obtain a mixture of isomers XIII and XIV,
yield 72%, bp 120 125 C (0.7 mm Hg). The mixture
was heated for 2 h at 160 C, after which 15 ml of 6N
HCl was added, the resulting mixture was stirred for
20 min, and the oily substance that floated was ex-
tracted with ether (3 5 ml). The aqueous phase was
refluxed for 6 h and evaporated in a vacuum. The dry
residue was dissolved in 6 ml of anhydrous ethanol,
and 0.25 g of propylene oxide was added. The pre-
cipitate that formed was filtered off to obtain 0.91 g
(60%) of aminophosphonic acid XXXIV, mp 227
(THF), P, ppm: 13.7. 19F NMR spectrum (THF),
,
F
ppm: 68.5 (3F, CFd3), 108.79 (1F, FC6H4). Fou
nd, %: N 4.12; P 8.43. C13H16F4NO4P. Calculated,
%: N 3.92; P 8.67.
Diethyl [1-(2,4-dichlorobenzoylamino)-2,2,2-tri-
fluoroethyl]phosphonate (XXXVIc). Yield 70%, mp
102 103 C. 1H NMR spectrum (CDCl3), , ppm:
1.34 t (6H, MeCH2), 4.21 m (4H, OCH2), 5.29 m (1H,
3
CHP), 7.20 d (1H, NH, JHH 8 Hz), 7.35 d (1H, Ph),
7.47 s (1H, Ph), 7.52 d (H, Ph). 31P NMR spectrum
(CHCl3):
13.33 ppm. 19F NMR spectrum (CHCl3):
P
68.0 ppm. Found, %: Cl 17.60; P 7.78. C13H15
FF3NO4P. Calculated, %: Cl 17.37; P 7.59.
Diethyl [1-(3,5-dinitrobenzoylamino)-2,2,2-tri-
fluoroethyl]phosphonate (XXXVId). Equimolar
amounts of aminophosphonate XXV, triethylamine,
and 3,5-dinitrobenzoyl chloride were mixed in ben-
zene at room temperature. A day later, the precipitate
that formed was filtered off, washed on the filter with
water from triethylamine hydrochloride, and crystal-
1
227.5 C. H NMR spectrum (D2O), , ppm: 3.83 d.d
2
3
(1H, CH2, JHP 15.5 Hz, JHF 8.6 Hz). 31P
NMR spectrum (D2O), P, ppm: 1.9 d.q, 2JPH 15.5 Hz,
3JPF 5.9 Hz. 19F NMR spectrum (D2O), F, ppm:
3
3
67.8 d.d, JFH 8.7 Hz, JPF 5.9 Hz. Found, %: C
13.68; H 3.04; F 31.79; N 7.79; P 17.28. C2H5F3
NO3P. Calculated, %: C 13.42; H 2.81; F 31.83; N
7.28; P 17.32.
1
lized from ethanol. Yield 71%, mp 132 133 C. H
NMR spectrum (CDCl3), , ppm: 1.29 t and 1.37 t
(6H, MeCH2), 4.22 m (4H, OCH2), 5.45 m (1H, CHP),
(N-Benzyl-2,2-dimethylpropanimidoyl)phos-
phonic acid (XXXV) is formed on handling of imido-
ylphosphonate VIId in air. mp 16073172 C. H NMR
3
9.20 s (3H, Ph), 9.26 d (1H, NH, JHH 9.6 Hz). 31P
12.34 ppm. 19F NMR
67.38 ppm. Found, %: P
1
NMR spectrum (CHCl3):
P
spectrum (acetone-d6):
spectrum (CD3OD), , ppm: 1.25 s (9H, Me), 4.11 s
F
(2H, CH3), 7.44 m (5H, Ph). 31P NMR spectrum
7.26. C13H15F3N3O8P. Calculated, %: P 7.22.
(CD3OD):
1.5 ppm. Found, %: N 5.46; P 12.01.
Diethyl [1-(3,4,6-trimethoxybenzoylamino)-
2,2,2-trifluoroethyl]phosphonate (XXXVIe). Equi-
molar amounts of aminophosphonate XXV, triethyl-
amine, and 3,4,5-trimethoxybenzoyl chloride were
heated in benzene at 50 60 C for 6 h. The precipitate
that formed was filtered off, and the solvent was
removed from the filtrate. The oily residue was
several times extracted with hot petroleum ether. The
oil that precipitated on cooling was dissolved in
ethanol, filtered, and the solvent was removed. The
residue was triturated with petroleum ether until crys-
P
C12H18NO3P. Calculated, %: N 5.49; P 12.13.
Diethyl (1-acylamino-2,2,2-trifluoroethyl)phos-
phonates XXXVIa XXXVIc. To a solution of amino-
phosphonate XXV in ether, equivalent amounts of
triethylamine and the corresponding benzoyl chloride
were successively added. A day later, the resulting
mixture was filtered, the solvent was removed from
the filtrate, and the residue was crystallized from
petroleum ether.
1
Diethyl (1-benzoylamino-2,2,2-trifluoroethyl)-
phosphonate (XXXVIa). Yield 86%, mp 93 94 C.
1H NMR spectrum (CDCl3), , ppm: 1.31 t and 1.37
t (6H, MeCH2), 4.22 m (4H, OCH2), 5.38 m (1H,
tals formed. Yield 33%. H NMR spectrum (CDCl3),
, ppm: 1.30 t and 1.38 t (6H, MeCH2), 3.88 s (3H,
MeO), 4.1 4.3 m (4H, OCH23), 5.31 m (1H, CHP),
3
6.8 d.d (1H, NH, JHH 9.5 Hz, JHP 3 Hz), 7.04 s (2H,
3
CHP), 6.03 d (1H, NH, JHH 9 Hz), 7.48 m (2H, Ph),
Ph). Found, %: P 7.21. C16H23F3NO7P. Calculated,
%: P 7.21.
7.57 m (1H, Ph), 7.8 m (2H, Ph). 31P NMR spectrum
(benzene), P, ppm: 13.0. 19F NMR spectrum,
ppm: 68.6. Found, %: N 4.20; P 9.17. C13H17F3F
NO4P. Calculated, %: N 4.13; P 9.13.
,
Diethyl [2,2,2-trifluoro-1-(2-thienylamino)-
ethyl]phosphonate (XXXVIf). A mixture of equi-
molar amounts of aminophosphonate XXV, triethyl-
amine, and 2-thiophenecarbonyl chloride was refluxed
in benzene for 4 h. The resulting mixture was filtered,
the solvent was evaporated, and the crystalline residue
Diethyl [2,2,2-trifluoro-1-(4-fluorobenzoyl-
amino)ethyl]phosphonate (XXXVb. Yield 79%, mp
94 95 C. H NMR spectrum (CDCl3), , ppm: 1.31 t
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 12 2004

SIGMATROPIC ISOMERIZATIONS IN AZAALLYL SYSTEMS: XXI.
1877
was washed on the filter with water and crystallized
from a petroleum ether benzene mixture. Yield 86%,
2. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Si-
nitsa, A.D., Phosphorus, Sulfur Silicon, 1990, vols.
49 50, p. 73.
mp 126.5 128 C. 31P NMR spectrum (CDCl3),
,
ppm: 1.27 t and 1.33 t (6H, MeCH2), 4.21 m (4H,
OCH2), 5.42 m (1H, CHP), 7.19 t (1H, thienyl), 7.82
d (1H, thienyl), 8.06 d (1H, thienyl), 8.48 d (1H, NH,
3. Kafarski, P. and Lejczak, B., Phosphorus, Sulfur
Silicon, 1991, vol. 83, p. 193; Kukhar, V.P., Solosho-
nok, V.A., and Solodenko, V.A., Phosphorus, Sulfur
Silicon, 1992, vol. 92, p. 239.
3JHH 10 Hz). 31P NMR spectrum (acetone-d6):
P
14.81 ppm. Found, %: P 8.61; S 9.60. C11H15F3
NO4PS. Calculated, %: P 8.97; S 9.29.
4. Aminophosphonic and Aminophosphinic Acids.
Chemistry and Biological Activity, Kukhar, V.P. and
Hudson, H.R., Eds., Chichester: Wiley, 2000.
N-[1-(Diethoxyphosphinoyl)-2,2,2-trifluoro-
ethyl]N -(3,4-dichlorophenyl)urea (XXXVIIa). Equi-
molar amounts of aminophosphonate XXV and 3,4-di-
chlorophenyl isocyanate were mixed in benzene. A
day later, the crystals that formed were filtered off and
5. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Si-
nitsa, A.D., Tetrahedron Lett., 1992, vol. 33, no. 5,
p. 691.
1
washed with benzene. Yield 83%, mp 198 201 C. H
6. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Si-
nitsa, A.D., Zh. Obshch. Khim., 1995, vol. 65, no. 12,
p. 1961.
NMR spectrum (CDCl3), , ppm: 1.33 t and 1.47 t
(6H, MeCH2), 4.23 m and 4.32 d.q (4H, OCH2), 5.11
3
m (1H, CHP), 7.04 d (1H, CHNH, JHH 11 Hz),
7. Sinitsya, O.A., Kolotilo, M.V., and Onys’ko, P.P.,
7.32 m (2H, Ph), 7.55 s (1H, Ph), 8.48 s (1H, NHAr).
31P NMR spectrum (CHCl3): P 14.72 ppm. Found, %:
Cl 16.83; P 7.52. C12H16Cl2F3N2O4P. Calculated, %:
Cl 18.76; P 7.32.
Ukr. Khim. Zh., 1998, vol. 64, no. 5, p. 47.
8. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., and Si-
nitsa, A.D., Zh. Obshch. Khim., 1989, vol. 59, no. 6,
p. 1274.
N-[1-(Diethoxyphosphinoyl)-2,2,2-trifluoro-
ethyl]-N -cyclohexylurea (XXXVIIb). Equimolar
amounts of aminophosphonate XXV and cyclohexyl
isocyanate were refluxed in benzene for 6 h. The
solvent was removed, and the oily residue was washed
with several portions of petroleum ether and precipi-
9. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Povolots-
kii, M.I., and Sinitsa, A.D., Zh. Obshch. Khim., 1989,
vol. 59, no. 7, p. 1682.
10. Correlation Analysis in Chemistry, Chapman, N.B.
and Shorter, J., Eds., New York: Plenum, 1978.
1
tated with water from ethanol. Yield 32%. H NMR
11. Sinitsa, A.D., Onys’ko, P.P., Kim, T.V., Kiseleva, E.I.,
and Pirozhenko, V.V., Zh. Obshch. Khim., 1986,
vol. 56, no. 12, p. 2681.
spectrum (CDCl3), , ppm: 1.11 m (3H, cyclohexyl),
1.31 t and 1.39 t (6H, MeCH2 + 1H, cyclohexyl),
1.63 m (4H, cyclohexyl), 1.90 m (2H, cyclohexyl),
3.61 m (1H, cyclohexyl), 4.12 m (4H, OCH2), 5.04 m
12. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Prokopen-
ko, V.P., and Sinitsa, A.D., Zh. Obshch. Khim., 1990,
vol. 60, no. 3, p. 523.
3
(1H, CHP), 5.87 d (1H, NH cyclohexyl, JHH 7 Hz),
3
6.67 d (1H, NH, JHH 10 Hz). Found,%: N 7.89; P
8.65. C13H24F3N2O4P. Calculated,%: N 7.77; P 8.59.
13. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Prokopen-
ko, V.P., and Sinitsa, A.D., Zh. Obshch. Khim., 1996,
vol. 66, no. 8, p.1283.
N-[1-(Diethoxyphosphinoyl)-2,2,2-trifluoro-
ethyl]-N -phenylthiourea (XXXVIIc). Equimolar
amounts of aminophosphonate XXV and phenyl iso-
thiocyanate were mixed at room temperature. A day
later, the crystalline material was thoroughly washed
14. Onys’ko, P.P., Kim, T.V., Kiseleva, E.I., Sinitsa, A.D.,
and Kornilov, M.Yu., Zh. Obshch. Khim., 1990, vol.
60, no. 6, p. 1304.
1
with petroleum ether. Yield 92%, mp 141 144 C. H
15. Xiao, J., Zhang, X., and Yuan, C., Heteroatom. Chem.,
NMR spectrum (CDCl3, external HMDS), , ppm:
1.77 m (6H, MeCH2), 4.67 d.q (4H, OCH2), 6.74 m
(1H, CHP), 7.40 8.10 m (5H, Ph), 8.53 d (1H, NH,
3JHH 10 Hz), 9.83 s (1H, NHPh). Found, %: N 7.71;
P 8.63; S 8.88. C13H18F3N2O3PS, Calculated, %: N
7.56; P 8.36; S 8.66.
1998, vol. 11, no. 7, p. 536.
16. Yuan, C. and Zhang, X., Heteroatom. Chem., 1998,
vol. 9, no. 2, p. 139.
17. Hansch, C., Leo, A., and Taft, R.W., Chem. Rev.,
1991, vol. 91, no. 2, p. 165.
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ONYS’KO et al.
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