Trichloropyruvate N-acylimines. reactions with phosphorus nucleophiles

Article abstract of DOI:10.1134/S1070363212060035

Reactions of N-aroyltrichloroethaneimines CCl3C(R)=NCOAr (II, R = COOMe, CN) with phosphorus nucleophiles were studied. The reaction of imines II with o-phenylenediethylamidophosphite proceeded as [4+1]-cycloaddition leading to formation of stable spirocy

Full text of DOI:10.1134/S1070363212060035

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 6, pp. 1058–1064. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Ya.Ya. Khomutnik, P.P. Onys’ko, Yu.V. Rassukanaya, A.G. Vlasenko, A.N. Chernega, V.S. Brovarets, S.G. Pil’o, A.D. Sinitsa, 2012,
published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 6, pp. 898–905.
Trichloropyruvate N-Acylimines.
Reactions with Phosphorus Nucleophiles
Ya. Ya. Khomutnik, P. P. Onys’ko, Yu. V. Rassukanaya, A. G. Vlasenko,
A. N. Chernega, V. S. Brovarets, S. G. Pil’o, and A. D. Sinitsa
Institute of Organic Chemistry of National Academy of Sciences of Ukraine, ul. Murmanskaya 5, Kiev, 02094 Ukraine
e-mail:onysko@rambler.ru
Received May 5, 2011
Abstract—Reactions of N-aroyltrichloroethaneimines CCl3C(R)=NCOAr (II, R = COOMe, CN) with
phosphorus nucleophiles were studied. The reaction of imines II with o-phenylenediethylamidophosphite
proceeded as [4+1]-cycloaddition leading to formation of stable spirocyclic phosphoranes. The structure of one
of them was proved by the XRD analysis. The reaction of imine II with acyclic P(III) derivatives [Ph3P,
Ph2POEt, (PhO)3P] also includes the formation of labile monocyclic phosphoranes which eliminate phosphine
oxide and undergo chlorotropic transfer leading to trichloroazadienes CCl2=C(R)N=C(Cl)Ar. The reaction of
imines II with (EtO)2POH in the presence of triethylamine leads to the formation of (EtO)2P(O)Cl and the
corresponding dichlorovinylamides CCl2=C(R)NHCOAr.
DOI: 10.1134/S1070363212060035
Scheme 1.
N-Acylamines are valuable highly reactive building
blocks in the synthesis of various nitrogen-containing
compounds [1–4]. Activated imines with the carboxyl
group at the imine carbon atom are of special interest
because their functionalization leads to derivatives of
α-amino acids exhibiting high biological activity. For
example, trifluoropyruvate N-acylamines easily react
with nucleophilic and dipolar reagents to form
biologically important derivatives of trifluoroalanine
[3, 5–7]. At the same time imines of trichloropyruvates
until recently were not practically studied because
preparative methods of their synthesis were lacking.
We have developed lately a convenient method for the
preparation of trichlotopyruvate N-acylimines from
dichlorovinylamides I (Scheme 1) [8]. It was shown
that these substances easily react with S-,O-,N-, and C-
nucleophiles to form functional derivatives of α-amino
acids containing trichloroalanine fragment. It turned
out that this method was sufficiently universal and was
suitable for the synthesis of previously unknown
nitriles of acyliminotrichloropropanoic acids II (R =
C≡N). In the work the synthesis is described of the
first representative of such compounds IIc and the
reactions of phosphorus nucleophiles with N-aroyl-
imines containing methoxycarbonyl (IIa, IIb) or
nitrile group at the imine carbon atom.
Cl
R
N
Cl
R
Me3SiCl, Et3N
O
O
Cl
Me3Si
Cl HN
Ar
Ar
Iа_Ic
Cl
Cl
R
N
C6H6, Cl2, 20°C
_Me3SiCl
R
N
Cl3C
Ar
O SiMe3
Ar
O
IIа_IIc
R = COOMe, Ar = Ph (a), 4-MeC6H4 (b) [8]; R = CN,
Ar = Ph (c).
Analysis of published data shows the variety of
pathways taken by the reaction of N-acyl-α-haloalkane-
imines with nucleophilic phosphorus derivatives [9]. In
particular, haloalkane acylimines can react with the
participation of the C=N bond, of haloalkyl fragment,
or heterodiene system C=N–C=O to give the products
of C- and/or N-phosphorylation which in their turn
often undergo further transformations [9]. The
direction of these reactions is very sensitive to the
nature of substituents at the azomethine bond, the
nature of phosphorus reagent, and halogen in the
haloalkyl fragment. For iminocarboxylates IIa, IIb and
1058

TRICHLOROPYRUVATE N-ACYLIMINES
1059
Scheme 2.
R
P
CCl3
N
O
O
O
R
Ar
+
N
P
NEt2
Cl3C
O
O
O
Ar
NEt2
IVа_IVc
IIа_IIc
R = COOMe, Ar = Ph (a), 4-MeC6H4 (b); R = CN, Ar = Ph (c).
III
nitrile IIc containing the system of heterodiene bonds
all the above-described directions are possible and the
result of the reaction with trivalent phosphorus com-
pounds is not evident.
that phosphoranes are suggested as transition states in
many reactions, in particular, of the enzymatic transfer
of the phosphoryl group important for biochemical
processes [10]. Only several examples of structural
data for spirophosphoranes were found in the literature
[11, 12, 13], and for bicyclic phosphoranes containing
P-C bond in spirocycle no data were known. Due to
that the investigation of specific features of spatial
arrangement of spirocyclic phosporane IV presents
doubtless interest. It is also important that the isolated
stereoisomer IVc according to 31P NMR data is
analogous to the preferably formed diastereomer A of
compounds IVa, IVb. Compound IVc crystallizes in
centrosymmetric space group. General view of
molecule is presented in the figure. Main bond lengths
and bond angles are listed in the table.
It was found that the direction of the reactions of
compounds IIa–IIc with phosphorus nucleophiles
significantly depends on the nature of the phosphorus
reagent. With cyclic amidophosphite III they react
according to the type of [4+1] cycloaddition leading to
the formation of stable pentacoordinate phosphorus
compounds IVa–IVc (Scheme 2).
Compounds IV are the representatives of the new
type of spirophosphoranes containing the fragments of
α-aminocarboxylic and α-aminophosphonic acids in
the oxazaphospholine cycle. They contain two chiral
centers and may exist as various diastereomers. It was
found that stereoselectivity of the process shown in
Scheme 2 depends on the nature of substituents in the
imine. Esters IIa, IIb in the reaction with phosphite III
form a mixture of two diastereomers IVa, IVb (δAP
–21.3 and –21.0 ppm, δBP –19.7 and –19.5 respectively,
A/B ~ 1.3 : 1 and 1.1 : 1 respectively). At the same
time nitrile IIc under the same conditions gives only
one diastereomer IVc (δP –21.7 ppm). Hence,
stereoselectivity of the reaction correlates with
electron-acceptor properties of substituents in imines
II: IIc > IIa > IIb. Note that in the initial step of the
reaction of compounds IIa–IIc with phosphite III the
appearance of a weak (10–15%) signals of phosphorus
nuclei (δP –25.5, –25.3 and –25.0 ppm respectively)
was observed in 31P NMR spectra. Within 24 h they
disappeared. These signals can also be attributed to
diastereomeric forms of phosphoranes IV. Stereomers
A and B of spirophosphoranes IVa, IVb are con-
formationally stable and under usual conditions do not
transform into one another. At the same time after one
washing of diastereomer mixture of compounds IVa
with ether solid phase is enriched with the isomer B
(A/B = 1:6), and the filtrate with isomer A (A/B = 7:1).
It is established that phosphorus atom in the
structure of molecule IVc has the distorted trigonal
bipyramide coordination with the atoms O1 and O3 in
the axial and O2, N2, and C15 atoms in the equatorial
positions. The distortion of trigonal bipyramide is
revealed in the decrease in the angle between the axial
bonds to 171.16(9)°, and also in the non-equivalence
of angles in the equatorial plane [angles O2P1N2,
O2P1C15, and N2P1C15 are 121.36(9)°, 124.19(9)°, and
113.98(0)° respectively]. Phosphorus atom is located
in the equatorial plane [sum of equatorial angles is
259.5(2)°]. N2 nitrogen atom has the planar trigonal
coordination [sum of bond angles id 359.9(5)°].
Five-membered P1O1C7N1C15 cycle has the
envelope conformation. C1C6N1C15 atoms are coplanar
(root-mean-square deviation of atoms from the plane
of heterocycle is 0.001 Å ), and the point of envelope
C15P1O1 forms with the above-mentioned plane an
angle equal to 11.69°.
In the 13C NMR spectrum spatial nonequivalence of
equatorial (O2) and axial (O3) oxygen atoms of
dioxaphospholane ring is revealed in the magnetic
nonequivalence of C8, C9, C10, and C13, C11 and C12
atoms of dioxyphenylene ring, and also in the
Structure of spirophosphorane IVc was unam-
biguously established by XRD analysis. It is known
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1060
KHOMUTNIK et al.
carbonyl one increases the rate of the reaction as well
as its stereoselectivity.
Reactions with acyclic phosphites and triphenyl-
phosphine. The reaction of heterodienes with the
acyclic derivatives of trivalent phosphorus Va-Vc also
proceeds through the formation of monocyclic phos-
phoranes VI, the unstable products of [4+1]
cycloaddition (Scheme 3). Even at room temperature
they undergo transformations including the cleavage of
oxazaphospholine cycle.
The rate of the formation and the stability of phos-
phoranes VI is determined by the nature of phosphorus
reagent. Thus, the reaction with triphenylphosphine Va
proceeds easily and selectively at room temperature in
benzene, but phosphorane VIa (δP –44.8 ppm) quickly
eliminates phosphine oxide VIIa. Nitrile ylide A
generated in this process is stabilized by 1,4-chloro-
tropic migration and converts in imidoyl chloride
VIIIa. Fifteen minutes after the beginning of the
reaction (benzene, 15°C) the ratio of compounds VIIa/
VIa is 100:4, and after 30 min according to 1H and 31P
NMR data the quantitative formation of triphenyl-
phospine oxide VIIa and imidoyl chloride VIIIa takes
place. The reaction with diphenylphos-phinite Vb
proceeds analogously. At the same time the weak
Main bond lengths (d, Å ) and bond angles (ω, deg) in the
molecule of compound IVc
General view of molecule of compound IVc (hydrogen
atoms are not shown).
Bond
d
Angle
O1P1O2
O1P1O3
O1P1N2
O1P1C15
O2P1O3
O2P1N2
O2P1C15
O3P1N2
O3P1C15
N2P1C15
P1O1C7
P1O2C8
P1O3C9
C7N1C15
C1C6C7
O1C7N1
O1C7C6
N1C7C6
O2C8C9
P1C15N1
ω
significant difference in coupling constants (JCP) of
these pairs of carbon nuclei with phosphorus: δCA 147.2
Cl1–C14
Cl2–C14
Cl3–C14
P1–O1
1.758(2)
1.765(2)
1.775(2)
1.712(1)
1.646(2)
1.684(2)
1.633(2)
1.929(2)
1.341(2)
1.379(2)
1.369(3)
1.279(3)
1.452(3)
1.488(3)
1.483(3)
1.136(3)
1.558(3)
1.480(3)
1.519(3)
1.519(4)
83.91(7)
171.16(8)
93.95(9)
85.81(8)
90.99(8)
121.36(9)
124.20(9)
94.87(9)
91.14(9)
114.0(1)
113.8(1)
113.4(1)
112.5(1)
110.2(2)
119.7(2)
121.1(2)
115.4(2)
123.4(2)
111.3(2)
107.3(1)
s, δCB 142.8 d, JCP 5.8 Hz (C8, C9); δCA 112.24 d, JCP
2
2
16.8 Hz, δCB 111.8 d, JCP 9 Hz (C10, C13); δCA 122.4 s,
3
δCB 124.4 s (C11, C12).
P1–O2
P1–O3
By the method of competing reactions we have
evaluated the relative reactivity of nitrile IIc and esters
IIa, IIb with respect to amidophosphite III. It was
found that after introduction of nitrile group in
substrates IIa, IIb instead of methoxycarbonyl one the
reaction with amidophosphite significantly accelerates
P1–N2
P1–C15
O1–C7
O2–C8
O3–C9
N1–C7
N1–C15
N2–C17
N2–C19
N3–C16
C14–C15
C15–C16
C17–C18
C19–C20
(kIIc/kIIa,
~ 10). Hence, the increase in electron-
IIb
acceptor properties of substituent R at the imine carbon
atom (σPCOOMe 0.39, σPCN 0.66) leads to the increase in
the rate of the process. The established effect of
substituents agrees with the fact that cycloaddition
shown in Scheme 2 proceeds stepwise. Nucleophilic
attack of the imine carbon atom with phosphite is the
rate-limiting stage, and the bipolar ion formed is
stabilized by the intramolecular cyclization. Hence, the
introduction of nitrile group instead of methoxy-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

TRICHLOROPYRUVATE N-ACYLIMINES
1061
Scheme 3.
Cl3C COOMe
II
N
PR12
+
R2
R12PR2
Vа_Vc
O
Ar
VIа_VId
Cl
N
COOMe
Ar
1,4-Cl
C
Cl3C
N
Ar
Cl2C
A
COOMe
O
VIIIа, VIIIb
R12PR2
VIIа_VIId
V, VII: R1 = R2 = Ph (a); R1 = Ph, R2 = EtO (b); R1 = R2 = PhO (c); VI: R1 = R2 = Ph, Ar = Ph (a), 4-MeC6H4 (b); R1 = Ph,
R2 = EtO, Ar = 4-MeC6H4 (c); R1 = R2 = PhO, Ar = 4-MeC6H4 (d); VIII: Ar = Ph (a), 4-MeC6H4 (b).
nucleophile triphenyl phosphite reacts significantly
slower. A day after mixing the reagents in benzene at
15°C in 31P NMR spectrum of reaction mixture
together with the signals of starting phosphite Vc the
signals of phosphorane VId (δP –45.7 ppm) and
triphenyl phosphate VIIc (δP –17.3 ppm) are observed,
VIIc/VId ratio being 2:1. The reaction completes only
in 5 days, and a set of by-products is accumulated in
the reaction mixture. From the preparative point of
view the reaction with triphenylphosphine is preferred
for the conversion of imines II in azadienes VIII.
group (pathway c) with the formation of phosphonates
XIII. According to NMR spectral data the ratio of the
directions a, b, and c is 1:0.76:0.1 (R = Et) and 1:1:0.5
(R=Me3Si) respectively. The increase in the yield of C-
phosphorylated product XIIIc in the reaction with
(diethyl)trimethylsilyl phosphite is due to the high
migration ability of trimethylsilyl group favoring the
transformation of the intermediate B in the product
XIIIc (Scheme 4). Spectral monitoring of dynamics of
this process confirms the proceeding of the reaction
through the intermediate formation of phosphoranes X.
For example, 15 min after the beginning of the reaction
of imine IIa with triethyl phosphite (benzene, 15°C)
signals of phosphorane X (R = Et, Ar = Ph)
(–35.7 ppm), of phosphorylated dichlorovinylamide
XIIa (–1.8 ppm), of triethyl phosphate XIa (0.6 ppm),
and of starting phosphite IXa (139.3 ppm) were
observed in 31P NMR spectrum. The ratio of these
signals was Xa:XIIa:XIa:IXa ~ 1.3:1:0.9:0.3. After
12 h the signals of triethyl phosphite and phosphorane
disappear and a weak signal of phosphonate XIIIa
(9.4 ppm) appears, the ratio XIIa:XIa:XIIIa being
1:0.8:0.1. The attribution of signals of compounds
XII,XIII in 31P NMR spectra was carried out on the
basis of comparison with the reported data [14, 15].
While using trialkyl or silyl phosphites new
pathways appear in the reaction. They are related to the
possible dealkylation of quasiphosphonium or phos-
phorane intermediates. It is established that the reac-
tion of imines II with phosphites IXa, IXb proceeds
non-selectively with the formation of products of N-
(XII) as well as of C-phosphorylation (XIII), and also
of phosphates XI. The obtained results can be
rationalized within the frames of Scheme 4.
The attack of phosphite on the most electrophilic
imine carbon atom of compounds II and the
subsequent intramolecular cyclization of the inter-
mediate bipolar ion B (pathway a) leads to phos-
phoranes X which transform in imidoyl chlorides
VIIIa, IIb analogously to Scheme 3. C,N-Migration of
phosphonium center in intermediate B (compare with
[9]) and the subsequent stabilization of carbanion C by
the elimination of ethyl or trimethylsilyl chloride leads
to the product of the aza-Perkow reaction XII (pathway
b). The stabilization of bipolar ion C may also be
achieved by O,N-migration of ethyl or trimethylsilyl
Reaction with hydrophosphoryl compounds. We
showed recently that N-, O-, or S-centrated X–H
nucleophiles even in the absence of base easily added
to the C=N bond of iminocarboxylates IIa, IIb with
the formation of functionalized derivatives of
trichloroalanine [1]. With diethyl hydrogen phosphite,
the P-centrated nucleophile, the reaction proceeds
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1062
KHOMUTNIK et al.
Scheme 4.
Cl3C COOMe
O
N
P(OEt)2
OR
+
(EtO)2P OR
VIIIа, VIIIb
O
Ar
XIа, XIb
X
а
R
O
O
O
IIа, IIb
(EtO)2P
N
Ar
b
N
Ar
Cl3C
COOMe
P(OEt)2
+
Cl2C C COOMe
(EtO)2P OR
Cl
OR
B
IXа, IXb
C
c
_RCl
O
O
O
R
N
Ar
(EtO)2P
Ar
N
Cl3C
COOMe
Cl2C
XIIа_XIIc
IX, XI: R = Et (a), Me3Si (b); XII, XIII: R = Et, Ar = Ph (a), 4-MeC6H4 (b); R = Me3Si, Ar = 4-MeC6H4 (c).
O
P(OEt)2
COOMe
XIIIа_XIIIc
more complex. In this case initially formed products of
addition to the C=N bond, phosphonates XIV (δP 9.6–
11.4 ppm), were found only spectroscopically
(compare with [9, 16]). Even at room temperature they
undergo ambiguous transformations including the
transfer of phosphoryl group and the formation of N-
and O-phosphorylated products [9, 14–16] (δP from
–5.4 to –5.9 ppm and from –8.4 to –8.9 ppm) and the
destruction of the latter (δP from –0.3 to –1.1 ppm).
Note also that the reaction of diethyl hydrogen
phosphite with more reactive nitrile IIc proceeds even
in low polar benzene. At the same time for performing
the reaction with iminocarboxylate IIb the presence of
dipolar solvent such as DMSO is necessary. In
benzene in the absence of a base no reaction takes
place. Hence, in the absence of bases the reaction of
imine II with diethyl hydrogen phosphite proceeds
non-selectively and cannot be used for the synthesis of
the corresponding phosphonates. As is known, the
catalysis with bases facilitates the nucleophilic
reactions of hydrophosphoryl compounds, in
particular, the Pudovik reaction. At the same time it
proved that using triethylamine principally changes the
pathway of the reaction of imines IIb, IIc with diethyl
hydrogen phosphite. In this case the formation of
diethyl chlorophosphate and dichlorovinylamides
Ib, Ic takes place (Scheme 5). Such unexpected route
of the reaction may be due to the elimination of diethyl
chlorophosphate from the adducts or to the halophilic
attack of phosphite ion on the positivated chlorine
atom of trichloromethyl group of the imines IIa–IIc.
Hence, reactions of N-aroyltrichloroethaneimines II
with nucleopilic P(III) derivatives depending on the
nature of substituents at phosphorus include [4+1]-
cycloaddition, addition to the C=N bond, and involv-
ing CCl3 group in the process. They can be also accom-
panied by rearrangements and degradation of the products.
EXPERIMENTAL
IR spectra were registered on an UR-20 spectro-
meter. NMR spectra were taken on a Varian VXR-300
(1H), Bruker Avance DRX-500 (1H, 13C), and Varian
Gemini-200 (31P) spectrometers with working
frequencies 299.95, 500.07, 125.76, and 81.03 MHz
respectively. Chemical shifts were measured with
respect to internal TMS (1H, 13C) and external 85%
H3PO4 (31P). All the reactions were carried out in
anhydrous conditions under argon.
XRD study of the single crystal of compound IVc
was carried out on an automatic Bruker Apex II
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

TRICHLOROPYRUVATE N-ACYLIMINES
1063
Scheme 5.
O
(EtO)2P
O
Not identified products
Ar
Cl3C
R
N
H
O
(EtO)2P
H
XIVb, XIVc
IIb, IIc
O
Cl
R
O
NEt3
+
(EtO)2P Cl
Cl HN
Ar
Ib, Ic
XIVb: R = COOMe, Ar = 4-MeC6H4; XIVc: R = CN, Ar = Ph.
diffractometer at –100°C. For the evaluation of
parameters of the unit cell and orientation matrix of the
crystal of compound IVb with linear dimensions
0.47×0.47×0.61 mm 9716 reflections with 2.20 < θ <
26.34° were collected. On the whole 22420 reflections
were collected among which 4478 were symmetrically
independent (averaging R-factor 0.028). Crystals of
compound IVa are monoclinic, a 11.4407(2), b 9.9134(2),
c 19.5542(4) Å, β = 97.602(1)°, V 2198.27(7) Å3, Z =
4, dcalc 1.471, μ 0.517 mm–1, F(000) 1000, space group
P21/n (no. 14). The structure was solved by the direct
method and refined by the root-mean-square method in
the full-matrix anisotropic approximation using the
CRYSTALS software [17]. In the refinement 3364
reflections were used with I > 3σ(I) (271 refined
parameter, number of reflections per parameter 12.4).
Chebyshev weight scheme was used with the coef-
ficients –9.10, –25.9, –22.3, –15.3, –5.84. All
hydrogen atoms were revealed objectively from the
Fourier difference series and included in refining with
the fixed heat and positional parameters. Final values
of scattering factors R 0.0378 and Rw 0.0321, GOF
1.0694 by the reflections with I > 3σ(I). Residual
electronic density from the differential Fourier series
0.75 and –0.63e/Å3. All crystallographic data were
deposited in the Cambridge structured bank, CCDC
814132.
hexane). IR spectrum (KBr), ν, cm–1: 1650, 1697 (C=N,
C=O), 2375 (C≡N). H NMR spectrum (CDCl3), δ,
1
ppm: 7.5 d (2H, 3JHH 7.4 Hz), 7.73 t (1H, 3JHH 7.5 Hz),
7.93 d (2H, 3JHH 7.5 Hz). 13C NMR spectrum (CDCl3),
δC, ppm: 91.78 (CCl3), 106.94 (C≡N), 129.26 (ipso C,
Ph), 129.34, 130.00 (o-C, m-C, Ph), 135.58 (p-C, Ph),
139.26 (C=N), 174.56 (C=O). Found, %: C 43.60, H
1.86, Cl 39.00, N 10.15. C10H5Cl3N2O. Calculated, %:
C 43.59; H 1.83, Cl 36.60; N 10.17.
2-Aryl-4-R-7,8-benzo-5-diethylamino-4-trichloro-
methyl-1,6,9-trioxa-3-aza-5-phosphaspiro[4.4]non-
2-enes (IVa–IVc). To a solution of 27.4 mmol of
imine II in 5 ml of anhydrous benzene 27.4 mmol of
amidophosphite III was added with stirring. Reaction
mixture was stirred for 12 h, the solvent was removed
in a vacuum and the residue was washed with petro-
leum ether.
7,8-Benzo-5-diethylamino-4-methoxycarbonyl-4-
trichloromethyl-2-phenyl-3-aza-1,6,9-trioxa-5-phos-
phaspiro[4.4]-non-2-ene (IVa). Yield 93%. IR spec-
trum (KBr pellet), ν, cm–1: 1640 (C=N), 1735 (C=O).
1H NMR spectrum (CDCl3), δ, ppm: diastereomer A:
1.04 t (3H, MeC, 3JHH 6.0 Hz), 1.42 t (3H, Me3C, 3JHH
6.9 Hz), 2.88–3.02 m (2H, NCH2), 3.05 s (3H, MeO),
3.64–3.85 m (2H, NCH2), 6.8–7.0 m (4H, OC6H4),
3
7.52 t (2H, 3,5 HPh, JHH 7.4 Hz), 7.61 t (1H, 4-HPh,
3
3JHH 7.4 Hz), 8.22 d (2H, 2,6-HPh, JHH 7.2 Hz);
N-Benzoyltrichloroacetimidoylcyanide (IIc). To
the solution of amide Ic, 27.4 mmol and trimethylchloro-
silane, 27.4 mmol, in 120 ml of anhydrous benzene
41.1 mmol of triethylamine was added with stirring.
After 2 days triethylamine hydrochloride was filtered
off and washed with 50 ml of benzene. To the filtrate a
solution of 100 mmol of chlorine in 30 ml of benzene
was added at 5–10°C. The obtained solution was stirred at
room temperature for 12 h, the solvent was evaporated
in a vacuum, and the residue was crystallized from
cyclohexane. Yield 87%, mp 105–110°C (from cyclo-
diastereomer B: 0.93 br. (3H, MeC), 1.13 br. (3H,
MeC), 2.7–3.0 m (2H, NCH3), 3.1-3.3 m (2H, NCH2),
3.91 s (3H, MeO), 6.9–7.1 m (4H, OC6H43), 7.50 t (2H,
3
3,5-HPh, JHH 7.4 Hz), 7.60 t (1H, 4-HPh, JHH 7.4 Hz),
3
31
8.22 d (2H, 2,6-HPh, JHH 7.2 Hz). P NMR spectrum
(CDCl3), δP, ppm: –21.3 (A), –19.7 (B). Found, %: C
48.49, H 4.29, Cl 20.35, N 5.35. C21H22Cl3N2O4P.
Calculated, %: C 48.53, H 4.27, Cl 20.46, N 5.39.
7,8-Benzo-5-diethylamino-4-methoxycarbonyl-2-
(4-tolyl)-4-trichloromethyl-3-aza-1,6,9-trioxa-5-phos-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012

1064
KHOMUTNIK et al.
phaspiro[4.4]-non-2-ene (IVb). Yield 88%. IR
spectrum (KBr pellet), ν, cm–1: 1630 (C=N), 1745
(C=O). 1H NMR spectrum (CDCl3), δ, ppm: diastereo-
cm–1: 1648 (C=N), 1736 (C=O). 1H NMR spectrum
(CDCl3), δ, ppm: 2.43 s (3H, MeC), 3.82 s (3H, OMe),
7.27 d (2H, Ar, 3JHH 7.4 Hz), 8.02 d (2H, Ar, 3JHH 7.4 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 21.60 (MeC),
52.87 (MeO), 122.25 (CCl2), 129.35, 129.72 (C2,C3,
Ar), 131.58 (=C–N), 135.03 (C1, Ar), 144.03 (C4, Ar),
150.09 (C=N), 161.03 (C=O). Found, %: C 47.24, H
3.12, Cl 34.07, N 4.10. C12H10Cl3NO2. Calculated, %:
C 47.01, H 3.29, Cl 34.69, N 4.57.
3
mer A: 1.03 t (3H, MeCH2, JHH 6.9 Hz), 1.42 t (3H,
3
MeCH2, JHH 6.9 Hz), 2.43 s (3H, MeAr), 2.88–3.02 m
(2H, NCH2), 3.03 s (3H, MeO), 3.65–3.85 m (2H,
NCH2), 6.82–7.02 m (4H, OC6H4), 7.30 d (2H, HTol,
3
3JHH 7.4 Hz), 8.08 d (2H, HTol, JHH 7.4 Hz);
diastereomer B: 0.92 br. (3H, MeCH2), 1.13 br. (3H,
MeCH2), 2.43 s (3H, MeAr), 2.7–3.0 m (2H, NCH2),
3.1–3.3 m (2H, NCH2), 3.90 s (3H, MeO), 6.83–7.03
REFERENCES
3
1. Weinreb, S.M. and Scola, P.M., Chem. Rev., 1989,
vol. 89, no. 7, p. 1525.
2. Weinreb, S.M. and Orr, R.K., Synthesis, 2005, no. 8,
p. 1205.
3. Osipov, S.N., Kolomiets, A.F., and Fokin, A.V., Usp.
Khim., 1992, vol. 61, no. 8, p. 1457.
m (4H, OC6H4), 7.30 d (2H, HTol, JHH 7.4 Hz), 8.08 d
3
(2H, HTol, JHH 7.4 Hz). 31P NMR spectrum (CDCl3),
δP, ppm: –21.0 (A), –19.5 (B). Found, %: C 49.61; H
4.52; Cl 19.85; N 5.21. C22H24Cl3N2O5P. Calculated,
%: C 49.50; H 4.52; C 19.85; N 5.21.
4. Levkovskaya, G.G., Drozdova, T.I., Rozentsveig, I.B.,
and Mirskova, A.N., Usp. Khim., 1999, vol. 68, no. 7,
p. 638.
5. Scerpos, H., Vorob’eva, D.V., Osipov, S.N., Odinets, I.L.,
Breuer, E., and Roschenthaler, G.-V., Org. Biomol.
Chem., 2006, vol. 4, no. 19, p. 3669.
6. Sewald, N., Riede, J., Bissinger, P., Burger, K., J. Chem.
Soc., Perkin Trans. 1, 1992, no. 3, p. 267.
7. Welch, J.T., Tetrahedron, 1987, vol. 43, no. 14, p. 3123.
8. Onys’ko, P.P., Khomutnik, Y.Y., Kim, T.N., Kyselyo-
va, O.L., Rassukana, Yu.V., Brovarets, V.S., and
Synytsya, A.D., Synthesis, 2011, no. 1, p. 65.
7,8-Benzo-5-diethylamino-4-trichloromethyl-2-
phenyl-4-cyano-3-aza-1,6,9-trioxa-5-phosphaspiro
[4.4]-non-2-ene (IVc). Yield 87%, colorless crystals,
mp 149–150°C (CH2Cl2-petroleum ether). IR spectrum
(KBr pellet), ν, cm–1: 1620 (C=N), 2380 (C≡N). 1H
3
NMR spectrum (C6D6), δ, ppm: 1.08 t (6H, Me, JHH
7 Hz), 2.8–3.0 m (2H, NCH2), 3.3–3.7 m (2H, NCH2),
6.8–6.9 m (1H, OC6H4), 6.96 d (2H, OC6H4, J 4.5 Hz),
7.13 d (1H, OC6H4, J 7.9 Hz), 7.33 t (2H, 3,5-HPh, 3JHH
3
~7.5 Hz), 7.39 t (1H, 4-HPh, JHH 7.3 Hz), 8.50 d (2H,
2,6-HPh, 3JHH 7.4 Hz). 13C NMR spectrum (CDCl3), δC,
ppm (numbering of C atoms see in the figure): 15.93
(CH3), 46.23 d (2JCP 3.5 Hz, CH2), 79.50 d (1JCP 151 Hz,
CP), 99.55 d (2JCP 6.8 Hz, CCl3), 111.75 d (3JCP 9 Hz)
and 112.24 d (3JCP 16.8 Hz) (C10, C13), 116.84 d (2JCP
1 Hz, C≡N), 122.43 and 124.39 (C11, C12), 129.30 d
(3JCP 1.5 Hz, C6), 129.5 and 129.5 (C1, C5, and C2, C4),
133.89 (C3), 142.77 d, (2JCP 5.8 Hz) and 147.20 s (C9
and C8), 165.66 d (2JCP 26.9 Hz, C≡N). 31P NMR
spectrum (CDCl3), δP, ppm: –21.7. Found, %: 48.39, H
3.40, Cl 22.57, N 8.95. C19H16Cl3N3O3P. Calculated,
%: C 48.38, H 3.42, Cl 22.55, N 8.91.
9. Onys’ko, P.P., Rassukana, Yu.V., and Sinitsa, A.D.,
Curr. Org. Chem., 2008, vol. 12, no. 1, p. 2.
10. Allen, K.N. and Dunaway-Mariano, D., Trends in
Biochem. Sci., 2004, vol. 29, no. 9, p. 495.
11. Chernega, A.N., Antipin, M.Yu., Struchkov, Yu.T.,
Gololobov, Yu.G., Boldeskul, I.E., Gusar’, N.I., and
Chaus, M.P., Zh. Strukt. Khim., 1984, vol. 25, no. 6, p. 93.
12. Abdrakhamanova, L.M., Mironov, V.F., Baronova, T.A.,
Dimukhametov, M.N., Krivolapov, D.V., Litvinov, I.A.,
Musin, R.Z., and Konovalov, A.I., Mendeleev
Commun., 2007, vol. 17, no. 5, p. 284.
13. Abdrakhamanova, L.M., Mironov, V.F., Baronova, T.A.,
Dimukhametov, M.N., Krivolapov, D.V., Litvinov, I.A.,
Balandina, A.A., Latypov, S.K., and Konovalov, A.I.,
Mendeleev Commun., 2005, vol. 16, no. 6, p. 320.
14. Kolotilo, N.V., Sinitsa, A.A., and Onys’ko, P.P., Izv.
Akad. Nauk, Ser, Khim., 1998, no. 10, p. 2101.
15. Rassukanaya, Yu.V., Sinitsa, A.A., and Onys’ko, P.P.,
Izv. Akad. Nauk, Ser, Khim., 2005, no. 11, p. 2567.
16. Kolotilo, N.V., Sinitsa, A.A., Rassukanaya, Yu.V., and
Onys’ko, P.P., Zh. Obshch. Khim., 2006, vol. 76, no. 8,
p. 1260.
Azadienes (VIII). To a solution of 0.5 mmol of
imine II in 3 ml of diethyl ether 0.5 mmol of tri-
phenylphosphine was added at 5–10°C. After 2 h the
precipitate of triphenylphosphine oxide was filtered
off, the residue was evaporated and extracted with
petroleum ether.
3-Methoxycarbonyl-1,4,4-trichloro-1-phenyl-2-
aza-1,3-diene (VIIIa) [18]. Yield 65%. IR spectrum,
ν, cm–1: 1648 (C=N), 1735 (C=O). Found, %: Cl
35.86. C11H8Cl3NO2. Calculated, %: Cl 36.36.
17. Watkin, D.J., Prout, C.K., Carruthers, J.R., and
Betteridge, P.W., CRYSTALS, issue 19, Chemical
Crystallography Laboratory, Univ. of Oxford.
18. Derach, B.S. and Mis’kevich, G.N., Zh. Org. Khim.,
1978, vol. 14, no. 5, p. 943.
3-Methoxycarbonyl-1-(4-tolyl)-1,4,4-trichloro-2-
aza-1,3-diene (VIIIb). Yield 63%. IR spectrum, ν,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012