Reactions of aldoketeniminophosphonates with CH-acids

Article abstract of DOI:10.1134/S1070363211040025

Aiming to obtain new polyfunctional organophosphorus compounds, we studied the reactions of aldoketeniminophosphonates with different CH-acids. The reactions were shown to proceed efficiently in anhydrous acetonitrile medium in the presence of the catalytic amounts of potassium carbonate to form the products of the addition of CH-acids to a multiple carbon-carbon bond followed by the prototropic isomerization to the corresponding γ-substituted β-functional alkylaminoethenephosphonates. The reaction of aldoketeniminophosphonates with CH-acids is found to depend significantly on the strength and nature of the acid. The formation of the carbon-carbon bond is possible mainly in the case of the CH-acids whose pK _a values lie within 10-14.

Full text of DOI:10.1134/S1070363211040025

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 628–638. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.I. Svintsitskaya, A.V. Dogadina, B.I. Ionin, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 4, pp. 534–545.
Reactions of Aldoketeniminophosphonates with CH-Acids
N. I. Svintsitskaya, A. V. Dogadina, and B. I. Ionin
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
е-mail: nsvincickaya@mail.ru
Received July 8, 2010
Abstract—Aiming to obtain new polyfunctional organophosphorus compounds, we studied the reactions of
aldoketeniminophosphonates with different CH-acids. The reactions were shown to proceed efficiently in
anhydrous acetonitrile medium in the presence of the catalytic amounts of potassium carbonate to form the
products of the addition of CH-acids to a multiple carbon-carbon bond followed by the prototropic
isomerization to the corresponding γ-substituted β-functional alkylaminoethenephosphonates. The reaction of
aldoketeniminophosphonates with CH-acids is found to depend significantly on the strength and nature of the
acid. The formation of the carbon–carbon bond is possible mainly in the case of the CH-acids whose pKa values
lie within 10–14.
DOI: 10.1134/S1070363211040025
Stable aldoketeniminophosphonates formed in the
reaction of chloroacetylenephosphonates with the
sterically hindered primary amines (tert-butyl-, 1-ada-
mantylamine) [1] are highly reactive compounds
whose structure contains several reaction centers,
which makes them attractive for the study of their
chemical properties. The addition to them of various
electrophilic and nucleophilic reagents is known [2].
However, aldoketenimines have not been brought into
the reactions with CH-acids, although the expected
adducts can be used as precursors for the synthesis of
open-chain and heterocyclic structures with biological
activity.
We found that aldoketeniminophosphonates react
readily with CH-acids in the presence of the catalytic
amount of K2CO3 with the quantitative formation of
the corresponding phosphonates of enamine structure.
Probably, the reaction proceeds as regioselective
nucleophilic addition to the multiple carbon–carbon
bond with an initial attack of the carbanion on the
diagonal carbon atom of aldoketenimine and the
subsequent prototropic imino-enamine isomerization.
The reaction occurs in the medium of anhydrous
acetonitrile at heating the equimolar amounts of the
initial reactants in the presence of the catalytic amount
of anhydrous potassium carbonate (~ 5 mol %) for 3–5 h.
CH3O
CH3O
CH3O
CH3O
CH3O
CH3CN
K2CO3
PCH=C=NR + XCH2Y
PCH2C NHR
XCY
IIа, IIb_IXа, IXb
PCH2C
XCHY
NR
CH3O
O
O
O
Iа, Ib
R = t-Bu (а), 1-Ad (b); X = Y = CN (II); X = Y = COOEt (III); X = CN, Y = COOEt (IV); X = CN, Y = SO2Ph (V);
O
X = CN, Y = (CH O) P(O) (VI); XCH Y=CH C(O)NHCH(COOEt) (VII); X = CN,
Y =
C
(VIII);
3
2
2
3
2
O
O
CH3
O
N
N
(IX).
XCH2Y =
O
CH3
628

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REACTIONS OF ALDOKETENIMINOPHOSPHONATES WITH CH-ACIDS
After the reaction completion, in the H–{31P}
NMR spectrum of the reaction mixture the signal of
the starting aldoketeniminophosphonate at δP ~ 25 ppm
disappears. An intense signal at δP ~ 21–23 ppm
appears, which indicates the formation of the adduct
with the assumed stucture. The obtained compounds
II–IX were purified from the minor tarring by the
column liquid chromatography on silica gel (MN
Kieselgel, 60/0.025–0.004 mm, eluent acetone–
petroleum ether, 1:3). The yield is almost quantitative.
The compounds II, V, and IX are colorless crystalline
substances, the others are very viscous colored liquids
which eventually crystallize.
In the 13C NMR spectrum of dimethyl 2-(1,3-
dimethyl-2,4,6-trioxohexahydro-5-pyrimidinylidene)-
2-tricyclo-[3.3.1.13,7]dec-1-ylaminoethanephosphonate
IXb (Fig. 2) the carbon atom directly attached to the
phosphorus resonates as a doublet signal at δC 31.21 ppm
with a large coupling constant with the phosphorus
1
1
nucleus J 137.9 Hz. The carbon atom at the double
bond (C2) resonates downfield at δC 167.56 ppm with a
small spin–spin coupling with the phosphorus nucleus
2J 5.2 Hz. The signal of the second carbon atom at the
double bond (C3) appears upfield at δC 90.73 ppm.
In the upfield region of the spectrum there are
intense singlet signals of the carbon atoms of the
adamantane fragment (δC 29–43 ppm) and a singlet
signals of the carbon atoms of two nonequivalent
methyl groups (δC ~ 27 ppm). The methoxy carbon
atoms appear at δC 53.19 ppm with a constant of spin–
spin coupling with the phosphorus nucleus 2JCP 6.0 Hz.
The quaternary carbon atom of adamantyl moiety is
recorded at δC 57.39 ppm. The carbonyl carbon atoms
C4, C4', and С5 resonate in a weak field with the
chemical shifts δC 163.15, 166.17, and 151.05 ppm,
respectively.
The 31P NMR spectrum of dimethyl 2-(1,3-
dimethyl-2,4,6-trioxohexahydro-5-pyrimidinylidene)-
2-tricyclo-[3.3.1.13,7]dec-1-ylaminoethanephosphonate
IXb contains a single signal at δP 22.93 ppm. The IR
spectra of the synthesized γ-functionally substituted β-
aminoalkenephosphonates II–IX contain intense bands
The structure of the compounds was confirmed by
the H, 13C, and 31P NMR spectroscopy. Thus, in the
1
1H NMR spectrum of dimethyl 2-(1,3-dimethyl-2,4,6-
trioxohexahydro-5-pyrimidinylidene)-2-tricyclo-
[3.3.1.13,7]dec-1-ylaminoethanephosphonate IXb
(Fig.1) 1), the methylene protons of the carbon atom
directly attached to the phosphorus appear as a doublet
signal in the strong field at δH 2.74 ppm (2JHP 20.8 Hz).
The signals of α-, β-, and γ-protons of the adamantane
fragment are observed upfield of other signals. The
methoxy protons resonate in the expected region, their
chemical shift is δH 3.77 ppm and the coupling
3
constant is JHP 11.2 Hz. An intense singlet in the
region of δH 3.27 ppm belongs to the protons of methyl
groups at the nitrogen atoms of barbituric acid. The
NH-proton resonates downfield at δH 9.12 ppm.
CH3
CH3O
PCH2
δ, ppm
1
Fig. 1. The H NMR spectrum of dimethyl 2-(1,3-dimethyl-2,4,6-trioxohexahydro-5-pyrimidinylidene)-2-tricyclo[3.3.1.13,7]dec-1-
ylaminoethanephosphonate IXb.
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SVINTSITSKAYA et al.
δС, ppm
Fig. 2. The 13C NMR spectrum of dimethyl 2-(1,3-dimethyl-2,4,6-trioxohexahydro-5-pyrimidinylidene)-2-tricyclo[3.3.1.13,7]dec-1-
ylaminoethanephosphonate IXb.
at 1550–1600 cm–1 corresponding to the carbon-carbon
double bond vibrations.
dimethyl 2-tert-butylamino-3,3-dicyanoprop-2-enephos-
phonate IIa (Fig. 3) was performed on a SMART-1000
CCD diffractometer (MoKα-irradiation, θ/2θ-scanning,
graphite monochromator). The crystals are monoclinic,
C11H18N3O3P; size 0.40×0.23×0.22 mm3; unit cell
parameters: a 8.6247(7), b 18.3866(16), c 9.6208(9) Å,
α 90, β 111.289(2), γ 90°, V 778.4(3) Å3, space group
P21/c, Z 4, dcalc 1.267 mg m–3. The structure was
solved by the direct method, the values of R-factor are
0.0520, RW 0.0959 [2349 reflections with I > 2σ(Ι)].
The hydrogen atoms were refined in the isotopic
approximation. All calculations were performed using
SHELXTL PLUS program package. Some bond
lengths and angles are given in Fig 3.
Note that in the case of the addition of diethyl
acetamidomalonate to N-tert-butyl- and N-adamantyl
(dimethoxyhosphoryl)ketenimine in the 13C NMR
spectrum of the product there are two duplicate signals
in the region of 125–130 ppm with constants of spin–
2
spin coupling with the phosphorus nucleus JCP 10–
12 Hz related to the resonance of the carbon atom at
the double bond (C2), which probably indicates the
formation of a mixture of syn- and anti-isomers.
13
In addition, the C NMR spectra of the adducts of
diethyl acetamidomalonate with N-tert-butyl- and N-
adamantyl(dimethoxyphosphoryl)ketenimines (VIIa,
VIIb) contain a peak of the carbon atom C3 of the CH-
acid residue as a signal of low intensity in the region
~ 60 ppm. Its location is confirmed by the fact that in
the case of such adduct of diethyl acetamidomalonate
to acetylenediphosphonate the carbon atom of CH-acid
appears as a doublet of doublets with a chemical shift
δC 69.0 ppm and spin–spin coupling constants with
two phosphorus nuclei 2JCP 15.2, 3JCP 20.9 Hz.
It should be noted that, unlike aminoacetylene-
phosphonates [3], in the case aldoketeniminophos-
phonates we were able to extend the range of the CH-
acids involved into the reaction. This fact confirms the
greater reactivity of the ketenimine in the reactions
with nucleophiles compared with ynamines.
The study showed that the reaction of
aldoketeniminophosphonates with the CH-acids is
affected by a number of factors, depending on the
nature of the CH-acid. We have found that the reaction
occurs mainly with the CH-acids with the pKa values
The structure of the substituted β-aminoalkene-
phosphonates was also confirmed by the X-ray diffrac-
tion analysis. The X-ray analysis of the crystal of
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REACTIONS OF ALDOKETENIMINOPHOSPHONATES WITH CH-ACIDS
Table 1. Parameters of the 1H, 13C, 31P NMR spectra of the 3-substituted 2-amino-2-propenephosphonates II–IX
X
1
2
3
(CH3O)2PCH2C
C
Y
O
HNR
1Н NMR spectrum, δ
(СН2Р), ppm,
(2JНР, Hz)
13С NMR spectrum
δС2, ppm, (2JСР, Hz)
Comp.
no.
31Р NMR spectrum,
δР, ppm
δС1, ppm, (1JСР, Hz)
δС3, ppm, (3JСР, Hz)
3.20 (22.4)
3.19 (22.0)
–
31.51 (135.3)
31.59 (137.4)
162.25 (5.7)
162.65 (8.9)
158.84 (6.7)
158.44 (7.1)
163.82 (6.1)
163.39 (6.7)
160.37 (5.5)
162.64 (4.2)
166.89 (6.2, 7.5)
166.456 (6.8, 5.8)
125.11 (12.2)
131.32 (10.92)
123.77 (12.43)
132.46 (8.9)
165.96 (7.2)
165.33 (6.7)
168.06 (4.7)
167.56 (5.2)
50.63
52.34
21.34
IIa
21.78
IIb
27.47 (134.7)
93.87 (5.6)
93.61 (3.9)
73.12
23.56
IIIа
IIIb
IVа
IVb
Vа
–
28.01 (139.1)
24.59
3.33 (22.8)
3.34 (22.8)
3.27 (22.8)
2.76 (20.0)
3.29 (22.8,
3.37 (23.2, 4JНР 1.9)
2.74 (22.4)
2.78 (22.6)
2.73 (20.41)
2.77 (22.0)
3.45 (22.8)
3.48 (24.0)
2.79 (22.4)
2.74 (20.8)
30.42 (135.1)
20.81
30.91 (136.1)
73.00 (4.6)
83.36 (6.9)
80.72 (2.7)
60.22 (5.6, 1JСР 199.8)
60.24 (7.5, 1JСР 204.9)
60.85
20.87
20.08
31.11 (133.4)
35.28 (130.6)
20.37
Vb
4JНР 1.8)
31.14 (134.3, 3JСР 12.5)
31.80 (134.9, 3JСР 11.7)
31.65 (137.0)
21.16 (7.4), 22.32 (7.4)
23.28 (5.3), 22.12 (4.8)
29.09
VIа
VIb
VIIа
32.56 (137.0)
61.64
28.17
VIIb
30.84 (139.8)
31.33 (134.9)
30.34 (135.3)
31.21 (138.0)
80.80
21.35
20.55
22.88
22.93
VIIIа
VIIIb
IXа
80.74 (2.7)
90.13
90.73
IXb
in the range of 10–14. Thus, an attempt to introduce
benzyl cyanide into the reaction does not lead to any
results that can be attributed to its low thermodynamic
CH-acidity (pKa 20.81), which is several orders of
magnitude lower than the acidity of the malonate (pKa
11–13). For the same reason, methylmalonic ester,
which has also a low ionization rate, does not react.
However, a similar result was obtained also in the
reaction of aldoketeniminophosphonates with the nitro
CH-acids (nitromalonic ester, ethyl nitroacetate, and p-
nitrobenzylcyanidemethane), whose thermodynamic
CH-acidity is very high; the inertness of the nitro
compounds in these reactions is associated with the
known fact of an abnormally low ionization rate,
which depends on the mechanism of the resonance
stabilization of the nitro carbanion. In the CH-acid
carbanion the charge is mainly localized on the more
electronegative atoms. As a result, both the proton
elimination and attachment to the carbon is slower than
in the case of CH-acids, where the carbanion charge is
mainly located on the carbon atom [4].
The acidity of the studied CH-acids was evaluated
using a program Marvin Sketch, Version 5.4.1
(ChemAxon.Ltd, http://chemaxon.com/marvin). The
pKa values calculated by this program for the CH-acids
correlate well with the published ones [4, 5] (Table 2).
Under these conditions we failed to perform the
reaction of aldoketeniminophosphonates with malonic
acid amide due to the low solubility of the latter in the
most organic solvents. The use of anhydrous
dimethylformamide and dimethyl sulfoxide for the
reaction was undesirable because of the possible
involvement of the solvent into the reaction and the
difficulties associated with the adducts isolation.
The reaction of aldoketeniminophosphonates with
malonic acid proceeds in another way. In this case
malonic acid reacts as an OH-acid (pKa 2.73) and aldo-
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SVINTSITSKAYA et al.
Table 2. рKа Values of CH-acids, calculated by Marvin Sketch program, Version 5.4.1
СН-Acid
O2NCH(COOEt)2
рKа
СН-Acid
CH2(CN)2
рKа
4.22
4.47
12.52
12.72
12.85
13.05
13.40
13.82
14.68
20.81
1,3-Dimethylbarbituric acid
CH2(CN)SO2Ph
CH2(CONH2)2
CH2(COOEt)2
CH2(NO2)COOEt
2-Furoylacetonitrile
CH3C(O)NHCH(COOEt)2
СH2(COOH)2
5.99
11.02
(CH3O)2P(O)CH2CN
CH2(CN)COOEt
CH3CH(COOEt)2
PhCH2CN
11.28
11.32
(2.73 O–H)
keteniminophosphonate acts as a strong dehydrating
agent. The reaction occurs predominantly as the hydra-
tion of acetylenic substrates. The reaction proceeds at
room temperature with a noticeable exothermic effect
to form the phosphonacetic acid alkylamides XIIIa–
XIIId, XIVa, XIVb.
O
P CH2C
P C CNR2
NR2
CH3CN
XIIIa_г
+ CH2(COOH)2
P CH
C
NR'
O
P CH2C
P : P(O)(OCH3)2
HNR'
XIVa, XIVb
H3C
CH(CH3)2
C2H5
C2H5
(a);
(c);
(d);
R' = t-Bu (a), 1-Ad (b).
N
(b); N
O
N
NR2:
N
CH(CH3)2
H3C
1
In the course of the reaction in the H–{31P} NMR
spectrum of the reaction mixture we observed the
appearance and growth of the signals of the products
of amide structure and the disappearance of the signals
of malonic acid. Thus, in the case of the reaction of
dimethyl morpholylethynephosphonate with malonic
acid in the NMR spectra of the reaction mixture taken
after the reaction completion and the solvent removal
there are only the signals corresponding to the dimeth-
oxyphosphorylacetic acid morpholylamide XIIIc. The
1H NMR spectrum of the reaction mixture contains the
upfield doublet signal of methylene protons of the
СН2Р fragment at δH 3.30 ppm (2JHP 22.0 Hz).
The methoxy protons appear at δH 3.75 ppm as a
doublet signal (3JHP 11.2 Hz). The protons of mor-
pholine moiety are unequal with respect to the
carbonyl oxygen atom and appear as two pairs of the
triplet signals with chemical shifts δH 3.50 and 3.58 ppm
(CH2N) and δH 3.60 and 3.66 ppm (CH2O) (3JHH
5.6 Hz), respectively.
Fig. 3. The general view of the molecule of dimethyl 2-
tert-butylamino-3,3-dicyanoprop-2-enephosphonate
IIa.
Selected bond lengths (Å) and angles (deg): Р1–С1 1.789,
N1–C2 1.327(2), C1–C2 1.513(3), C2–C3 1.390(3), N3–C5
1.148(3), C3–C5 1.436(3), C2N1C6 133.40(18), C2C1P1
111.77(13), N1C2C3 129.75(19), N1C2C1 112.90(17),
C3C2C1 117.34(17), C2C3C5 127.92(19).
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REACTIONS OF ALDOKETENIMINOPHOSPHONATES WITH CH-ACIDS
δС, ppm
Fig. 4. The 13C NMR spectrum of the reaction mixture of morpholylethynedimethylphosphonate with malonic acid.
The 13C NMR spectrum of the reaction mixture
contains a characteristic doublet signal of the carbon
atom C1 directly bonded to the phosphorus atom
located in a strong field at δC 31.68 ppm with a
constant of spin–spin coupling with the phosphorus
A similar course is observed in the reaction
between aldoketeniminophosphonates and nitromalo-
nates or nitroacetates. Owing to the high pKa values of
the nitro compounds the reaction occurs almost
1
immediately after the reagents mixing. The H, 13C,
1
nucleus JCP 134.7 Hz (Fig. 4). Two singlet signals of
and 31P NMR spectroscopy could detect reliably in the
reaction mixture the formation of the products of
amide structure. As with malonic acid, we failed to
determine the structure of the end-products of de-
hydration of the nitro-containing CH-acids.
equal intensity in the region of δC 42.16 and 47.05 ppm
correspond to the unequal carbon atoms of the
morpholine fragment attached directly to the nitrogen
atom. The carbons of CH2O-morpholine group are
recorded as an intense singlet signal with the chemical
shift δC 66.29 ppm. The CH3OP-carbon atoms resonate
with the chemical shift δC 53.40 ppm (2JCP 5.4 Hz).
The carbonyl carbon atom appears downfield at δC
163.10 ppm (2JCP 3.4 Hz).
It should be noted that in the reaction of
nitromalonates and nitroacetates with N-tert-butyl
(dimethoxyphosphoryl)ketenimine we observed the
preferential formation of the phosphonoacetic acid
nitrile together with the corresponding amide, which
1
Note that in the NMR spectra of the reaction
mixture there are no signals corresponding to the initial
was confirmed by the H, 13C, and 31P NMR spec-
troscopy. Thus, after the removal of the solvent and the
starting CH-acid the 1H NMR spectrum of the reaction
mixture contained the upfield doublet signal of the
13
malic acid, but in the C NMR spectrum in the strong
and weak field there are two low-intensity singlet
signals with the chemical shifts δC 20.54 and
172.98 ppm, respectively, which can probably be
attributed to the dehydration product of malonic acid.
But we have not succeeded to establish structure of
these products unequivocally.
2
CH2P-protons (δH 2.72 ppm, JHP 20.8 Hz) of the
amide product along with the intense doublet with
(2
chemical shift δH 2.89 ppm JHP 20.41 Hz) belonging
to the CH2P-protons of the second product, the
phosphonoacetic acid nitrile.
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SVINTSITSKAYA et al.
CH3OP
PCH2
(CH3O)2PCH2CN
O
O
(CH3O)2PCH2C
HNC(CH3)3
O
δС, ppm
Fig. 5. The 13C NMR spectrum of the reaction mixture of N-tert-butyl(dimethoxyphosphoryl)ketenimine with diethyl nitromalonate.
The 13C NMR spectrum of the reaction mixture
(Fig. 5) contains the characteristic doublet signals of
the carbon atoms C1 directly attached to the phos-
phorus atom in both reaction products: In a strong field
there is an intense doublet at δC 14.99 ppm (1JCP 143.6 Hz)
corresponding to the nitrile carbon resonance, the
amide carbon C1 resonates with the chemical shift δC
35.00 ppm (1JCP 131.3 Hz). The signals of tert-butyl
group appear upfield: An intense singlet signal at δC
28.26 ppm corresponds to the resonance of the methyl
groups, and a singlet signal at δC 51.35 ppm belongs to
the quaternary carbon atom. In the region of ~ 53 ppm
there are two doublet signals corresponding to the
resonance of CH3OP-carbon atoms. The doublet of
lower intensity δC 52.99 ppm (2JCP 5.5 Hz) is assigned
to the reaction product of amide structure. The
methoxy groups of phosphonoacetic acid nitrile appear
as the more intense doublet with the chemical shift δC
53.96 ppm (2JCP 7.8 Hz). An intense doublet signal
A similar result, the nitrile formation, was observed
in the reaction of N-tert-butyl(dimetilphosphono)keten-
imine with mineral acids, such as hydrogen chloride.
As noted in [6], the reaction proceeds through the
proton attack of the imine nitrogen of ketenimino-
phosphonate to form the adduct at the double nitrogen-
carbon bond followed by stabilization via the tert-butyl
group elimination (t-BuCl or isobutylene) to give
phosphonoacetic acid nitrile.
Thus, aldoketeniminophosphonates were estab-
lished to react with the CH-acids, the pKa values of
which lie within 10–14, to afford the γ-functionally
substituted β-aminoalkenephosphonates.
EXPERIMENTAL
The NMR spectra were recorded on spectrometers
Bruker AC-200 operating at 200.132 (1H), 50.328
(13C), and 81.014 (31P) MHz, Bruker AC-400 operating
at 400.133 MHz (1H), and Tesla BS-497 (100 MHz)
2
downfield (δC 112.79 ppm, JCP 10.6 Hz) corresponds
1
using the double magnetic resonance H–{31P} tech-
to the resonance of the carbon atom of nitrile group.
The carbonyl carbon of N-tert-butylamide is registered
downfield at δ C 163.18 ppm (2JCP 5.7 Hz).
The 31P NMR spectrum of the reaction mixture is
represented by two signals at δP 17.33 (nitrile) and
25.27 ppm (amide). The integral intensities ratio is 5:1.
1
nique. In the H NMR spectra hexamethyldisiloxane
(HMDS) was used as an internal reference. The
phosphorus chemical shifts were determined relative to
external 85% phosphoric acid (Bruker AC-200) and
trimethylphosphate (Tesla BS-497). The 13C spectra
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REACTIONS OF ALDOKETENIMINOPHOSPHONATES WITH CH-ACIDS
were recorded relative to the internal CDCl3 and
DMSO-d6. The IR spectra were recorded on a
Shimadzu FTIR-8400S instrument from KBr pellets.
colored liquid. The target products were chromato-
graphed by the liquid chromatography on silica gel
(MN Kieselgel, 60/0.025–0.004 mm), eluent carbon
tetrachloride–acetone, 4:1. The product yield was
almost quantitative.
The standard laboratory techniques were used in
purifying and drying the organic solvents and reagents
[7–9].
Dimethyl 2-tert-butylamino-3,3-dicyano-2-propene-
phosphonate (IIa) was prepared according to the
general procedure from 1 g of N-tert-butyl(dimethoxy-
phosphoryl)ketenimine and 0.32 g of malonic acid
dinitrile. The product was isolated by recrystallization
from benzene. IR spectrum, ν, cm–1: 1238 (P=O), 1569
N-tert-Butyl(dimethoxyphosphoryl)ketenimine (Ia).
To a solution of 2.9 g of tert-butylamine in 50 ml of
anhydrous diethyl ether was added dropwise 3.4 g of
dimethyl chloroacetylenephosphonate at stirring and
cooling in the range of –5 to –10°C. The reaction
mixture was kept at room temperature for 2 h, then
tert-butylamine hydrochloride was filtered off and
washed with ether (5×5 ml). The filtrate was
concentrated and distilled in a vacuum. Yield 4.3 g
(98%), bp 65–66°С (1 mm Hg) [2]. 1 H NMR spectrum
(CDCl3), δH, ppm: 1.17 s (9H, CH3), 3.21 d (1H, PCH,
1
(C=C), 2190 and 2206 (C≡N). H NMR spectrum
(CDCl3), δH, ppm: 1.51 s (9H, CH3), 3.20 d (2H, CH2P,
2JHP 22.4 Hz), 3.82 d (6H, CH3OP, 3JHP 11.2 Hz), 6.61
13
br.s (1H, NH). C NMR spectrum (CDCl3), δC, ppm:
30.77 [C(CH3)3], 31.51 d (CH2P, 1JPC 135.3 Hz), 50.63
2
[=C(CN)2], 53.66 d (CH3OP, JCP 5.1 Hz), 56.32
[C(CH3)3], 116.13 (C≡N), 162.25 d (=CN, 2JCP 5.7 Hz).
31P NMR spectrum (CDCl3): δP 21.34 ppm. Found, %:
C 49.01; H 6.90; N 15.88. C11H18N3O3P. Calculated,
%: C 48.71; H 6.69; N 15.49.
3
2JHP 3.2 Hz), 3.61 d (6H, CH3OP, JHР 12.0 Hz). 13C
NMR spectrum (CDCl3), δC, ppm: 30.00 [C(CH3)3],
1
2
34.89 d (PCH, JCP 211.9 Hz), 52.41 q (CH3OP, JCP
4.5 Hz), 59.92 [C(CH3)3], 167.90 d (C=N, 2JCP 6.8 Hz).
31P NMR spectrum (CDCl3): δP 26.47 ppm.
Dimethyl 2-(1-adamantylamine)-3,3-dicyano-2-
propenephosphonate (IIb) was prepared according to
the general procedure from 1 g of N-(1-adamantyl)-
(dimethoxyphosphoryl)ketenimine and 0.23 g of
malonic acid dinitrile. The product was isolated by recrys-
N-Adamantyl(dimethoxyphosphoryl)ketenimine
(Ib). To a solution of 4.3 g of 1-adamantylamine in
60 ml of anhydrous diethyl ether was added dropwise
1.7 g of dimethyl chloroacetylenephosphonate at
stirring and cooling to 0–5°C. The reaction mixture
was kept at room temperature for 24 h. The precipitate
was filtered off and washed with ether (5×5 ml). The
filtrate was concentrated to oil. Yield 2.79 g (99%) [2].
1H NMR spectrum (CDCl3), δH, ppm: 1.64–1.87 m
(12H, CH2, adamant.), 2.00–2.12 m (3H, CH,
1
tallization from benzene. H NMR spectrum (CDCl3),
δH, ppm: 1.69 m (6H, γ-CH2, adamant.), 2.10 m (6H,
α-CH2, adamant.), 2.36 m (3H, β-CH, adamant.) 3.19 d
2
3
(2H, CH2P, JHP 22.0 Hz), 3.77 d (6H, CH3OP, JHP
10.8 Hz), 6.60 br.sс (1H, NH). (1H, NH). 13C NMR
spectrum (CDCl3), δC, ppm: 29.52 (CH, adamant.),
1
2
31.59 d (CH2P, JPC 137.4 Hz), 35.37 γ-CH2,
adamant.), 3.36 d (PCH, JCP 2.0 Hz), 3.70 d (6H,
3
CH3OP, JHP 8.10 Hz). 13C NMR spectrum (CDCl3),
adamant.), 42.98 α-CH2, adamant.), 52.34 [=C(CN)2],
53.67 d (CH3OP, 2JCP 3.6 Hz), 57.56 (C–N, adamant.),
116.13 (C≡N ), 162.65 d (=CN, 2JCP 8.9 Hz). 31P NMR
spectrum (CDCl3): δP 21.78 ppm.
1
δC, ppm: 29.26 (CH, adamant.), 34.26 d (PCH, JCP
212.9 Hz), 35.40 γ-CH2, adamant.), 43.04 (α-CH2,
adamant.), 52.07 d (CH3OP, 2JCP 5.6 Hz), 59.74 (C–N,
2
adamant.), 167.88 d (C=N, JCP 8.4 Hz). 31P NMR
Dimethyl 2-tert-butylamino-3-cyano-3-ethoxy-
carbonyl-2-propenephosphonate (IIIa) was prepared
according to the general procedure from 1 g of N-tert-
butyl(dimethoxyphosphoryl)ketenimine and 0.55 g of
ethyl cyanoacetate. IR spectrum, ν, cm–1: 1276 (P=O),
spectrum (CDCl3): δP 26.18 ppm.
Functional γ-substituted β-tert-butyl(1-ada-
mantyl)aminoalkenephosphonates (IIa–IXa, IIb–
IXb). General procedure. To a solution of 0.0049 mol
of the corresponding aldoketeniminophosphonate in
5 ml of anhydrous acetonitrile was added 0.0049 mol
of CH-acid and catalytic amount (0.03 g) of anhydrous
potassium carbonate. The reaction mixture was kept
for several hours at 80°C at exclusion of the air
moisture. The solvent was evaporated under the
vacuum of a water-jet pump, the residue was a viscous
1
1608 (C=C), 1659 (C=O), 2205 (C≡N). H NMR
spectrum (CDCl3), δH, ppm: 1.27 m (3H, CH3CH2O,
3JHN 7.4 Hz), 1.45 s [9H, C(CH3)3], 3.33 d (2H, CH2P,
2JHP 22.8 Hz), 3.80 d (6H, CH3OP, 3JHP 11.2 Hz), 4.15
q (2H, OCH2CH3, 3JHH 7.4 Hz), 10.44 br.s (1H, NH).
13C NMR spectrum (CDCl3), δC, ppm: 14.13
1
(CH3CH2O), 30.42 d (CH2P, JPC 135.1 Hz), 30.88
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SVINTSITSKAYA et al.
2
2
[C(CH3)3], 53.18 d (CH3OP, JCP 6.0 Hz), 55.18
[C(CH3)3], 60.18 (OCH2CH3), 73.12 [=C(CN)COO·
CH2CH3], 118.61 (C≡N), 163.82 d (=CN, 2JCP 6.1 Hz),
168.67 (C=O). 31P NMR spectrum (CDCl3): δP 20.81
ppm. Found, %: C 49.41; H 7.16; N 8.52.
C13H23N2O5P. Calculated, %: C 49.05; H 7.28; N 8.80.
α-CH2, adamant.), 52.91 d (CH3OP, JCP 5.6 Hz),
54.80 (C–N, adamant.), 59.68 (OCH2CH3), 93.58
[=C(COOCH2CH3)2, 3JCP 4.4 Hz], 158.54 d (=CN, 2JCP
7.3 Hz), 168.98 (C=O). 31P NMR spectrum (CDCl3):
δP 24.59 ppm.
Dimethyl 2-tert-butylamino-3-cyano-3-phenyl-
sulfonyl-2-propenephosphonate (Va) was prepared
according to the general procedure from 1 g of N-tert-
butyl(dimethoxyphosphoryl)ketenimine and 0.89 g of
phenylsulfonylacetonitrile. The reaction product was
isolated by recrystallization from benzene. H NMR
spectrum (CDCl3), δH, ppm: 1.50 s [9H, C(CH3)3], 3.27
d (2H, CH2P, JHP 22.8 Hz), 3.69 d (6H, CH3OP, JHP
12.0 Hz), 7.55 m (2H, CHm, 3JHH 7.4 Hz), 7.63 m (1H,
CHp, 3JHH 7.4 Hz), 8.00 d (2H, CHo, 3JHH 7.4 Hz), 8.95
Dimethyl 2-(1-adamantylamino)-3-cyano-3-ethoxy-
carbonyl-2-propenephosphonate (IIIb) was prepared
according to the general procedure from 1 g of N-(1-
adamantyl)(dimethyphosphono)ketenimine and 0.40 g
1
1
of ethyl cyanoacetate. H NMR spectrum (CDCl3), δH,
3
ppm: 1.24 m (3H, CH3CH2O, JHH 7.2 Hz), 1.62 m
2
3
(6H, γ-CH2, adamant.) 1.97 m (6H, α-CH2, adamant.),
2
2.09 m (3H, β-CH, adamant.), 3.19 d (2H, CH2P, JHP
3
22.8 Hz), 3.78 d (6H, CH3OP, JHP 10.8 Hz), 4.12 q
3
13
(2H, OCH2CH3, JHH 7.2 Hz), 10.28 br.sс (1H, NH).
br.s (1H, NH). C NMR spectrum (CDCl3), δC, ppm:
(1H, NH). 13C NMR spectrum (CDCl3), δC, ppm: 14.11
(CH3CH2O), 29.34 (CH, adamant.), 31.91 d (CH2P,
1JPC 13.1 Hz), 35.42 γ-CH2, adamant.), 43.39 α-CH2,
adamant.), 53.19 d (CH3OP, 2JCP 7.2 Hz), 56.57 (C–N,
adamant.), 60.15 (OCH2CH3), 73.00 [=C(CN)COO·
CH2CH3], 118.69 (C≡N), 163.39 d (=CN, 2JCP 6.7 Hz),
168.67 (C=O). 31P NMR spectrum (CDCl3): δP 20.87 ppm.
31.11 d (CH2P, 1JPC 133.4 Hz), 31.21 [C(CH3)3], 53.34
2
d (СН3ОР, JСP 6.7 Hz), 56.34 [C(CH3)3], 83.36 [=C
3
(CN)SO2Ph, JСP 6.9 Hz], 116.51 (С≡N), 126.43
(CHm), 129.17 (CНо), 133.34 (Сp), 141.93 (SO2C, Ph),
160.37 d (=СN, JСP 5.5 Hz). 31P NMR spectrum
2
(CDCl3): δP 20.08 ppm.
Dimethyl 2-(1-adamantylamine)-3-cyano-3-phenyl-
sulfonyl-2-propenephosphonate (Vb) was prepared
according to the general procedure from 1 g of N-(1-
adamantyl)(dimethyphosphono)ketenimine and 0.63 g
of phenylsulfonylacetonitrile. The reaction product
Dimethyl 2-tert-butylamino-3,3-diethoxycarbonyl-
2-propenephosphonate (IVa) was prepared according
to the general procedure from 1 g of N-tert-butyl
(dimethoxyphosphoryl)ketenimine and 0.78 g of
1
1
diethyl malonate. H NMR spectrum (CDCl3), δH,
was isolated by recrystallization from benzene. H
3
ppm: 1.25 br.s (3H, CH3CH2O, JHH 7.2 Hz), 1.47 s
NMR spectrum (CDCl3), δH, ppm: 1.67 m (6H, γ-CH2,
adamant.), 1.99 m (6Н, α-СН2, adamant.), 2.06 m (3Н,
[9H, C(CH3)3], 3.70 d (6H, CH3OP, 3JHP 10.8 Hz), 4.12
3
2
br.q (2H, OCH2CH3, JHH 7.2 Hz), 10.18 br.s (1H,
β-СН, adamant.), 2.76 d (2H, СН2Р, JHP 20.4 Hz),
NH). 13C NMR spectrum (CDCl3), δC, ppm: 03.14
3.78 d (6Н, СН3ОP, JHP 11.6 Hz), 7.64 t (2Н, СНm,
3
1
3
(CH3CH2O), 27.47 d (CH2P, JPC 134.7 Hz), 31.48
3JHH 7.6 Hz), 7.77 t (1Н, СНp, JHH 7.6 Hz), 8.02 d
2
3
13
[C(CH3)3], 53.02 d (CH3OP, JCP 5.3 Hz), 53.59
(2Н, СНо, JHH 7.6 Hz), 6.22 br.s (1H, NH). C NMR
[C(CH3)3], 59.82 (OCH2CH3), 93.87 [=C(COOCH2CH3)2,
spectrum (CDCl3), δC, ppm: 29.45 (СН, adamant.),
35.28 d (СH2P, JPC 130.6 Hz), 35.46 (γ-СН2,
2
1
3JCP 5.7 Hz], 158.84 d (=CN, JCP 6.7 Hz), 169.11
(C=O). 31P NMR spectrum (CDCl3): δP 23.56 ppm.
adamant.), 43.27 (α-СН2, adamant.), 52.23 d (СН3ОР,
2JСP 5.4 Hz), 57.30 (C–N, adamant.), 80.72 [=C(CN)
Dimethyl 2-(1-adamantylamino)-3,3-diethoxycar-
bonyl-2-propenephosphonate (IVb) was prepared
according to the general procedure from 1 g of N-(1-
adamantyl)(dimethyphosphono)ketenimine and 0.56 g
3
SO2Ph, JСP 2.7 Hz], 118.65 (С≡N), 126.06 (CHm,
arom.), 130.61 (CНо, arom.), 135.16 (Сp, arom.),
2
142.25 (SO2C, arom.), 162.64 d (=СN, JСP 4.2 Hz).
31P NMR spectrum (CDCl3): δP 21.35 ppm.
1
of diethyl malonate. H NMR spectrum (CDCl3), δH,
3
ppm: 1.22 m (3H, CH3CH2O, JHH 7.6 Hz), 1.62 m
Dimethyl 2-tert-butylamino-3-cyano-4-(2-furyl)-
4-oxo-2-butenephosphonate (VIa) was prepared
according to the general procedure from 1 g of N-tert-
butyl(dimethoxyphosphoryl)ketenimine and 0.66 g of
(6H, γ-CH2, adamant.) 1.96 m (6H, α-CH2, adamant.),
2.25 m (3H, β-CH, adamant.), 3.71 d (6H, CH3OP,
3
3JHP 11.2 Hz), 4.14 q (2H, OCH2CH3, JHH 7.6 Hz),
5.10 br.s (1H, NH). 13C NMR spectrum (CDCl3), δC,
ppm: 13.93 (CH3CH2O), 28.01 d (CH2P, 1JPC 139.1 Hz),
29.39 (CH, adamant.), 35.65 γ-CH2, adamant.), 43.90
furoylacetonitrile. H NMR spectrum (CDCl3), δH,
1
2
ppm: 1.51 s [9H, С(CH3)3], 3.45 d (2H, СН2Р, JHP
22.8 Hz), 3.82 d (6Н, СН3ОP, 3JHP 11.6 Hz), 6.45–6.49
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REACTIONS OF ALDOKETENIMINOPHOSPHONATES WITH CH-ACIDS
3
m (2Н, β-СН, furan.), 7.54 d (1Н, α-СН, furan., JHH
3.2 Hz), 13.05 br.s (1H, NH). 13C NMR spectrum
(CDCl3), δC, ppm: 30.81 [C(CH3)3], 30.84 d (СH2P,
dure from 1 g of N-(1-adamantyl)(dimethyphosphono)-
ketenimine and 0.76 g of diethyl acetamidomalonate.
1H NMR spectrum (DMSO-d6), δH, ppm: 1.20 t (3H,
1JPC 139.8 Hz), 53.36 d (СН3ОР, JСP 5.7 Hz), 56.15
CH3CH2О, JHН 7.6 Hz), 1.24 t (3H, CH3CH2О, JHН
7.6 Hz), 1.63 m (6H, γ-CH2, adamant.), 1.97 m (6Н, α-
СН2, adamant.), 2.08 m (3Н, β-СН, adamant.), 2.04 s
2
3
3
[C(CH3)3], 80.80 [=C(CN)С(O)Fu], 111.76 (С≡N),
117.51 (β'-СН, furan.), 120.62 (β-CH, furan.), 145.60
(α'-CН, furan.), 150.62 (α-С, furan.), 165.96 d (=СN,
2JСP 7.2 Hz), 177.28 (C=O). 31P NMR spectrum
(CDCl3): δP 21.35 ppm.
2
(3H, CH3C=O), 2.73 d (2H, СН2Р, JHP 20.4 Hz), 2.77
2
3
d (2H, СН2Р, JHP 22.0 Hz), 3.75 d (6Н, СН3ОP, JHP
10.8 Hz), 3.77 d (6Н, СН3ОP, 3JHP 11.2 Hz), 4.16 br.q
(2Н, ОСН2СН3, JHН 7.6 Hz), 4.23 br.q (2Н,
3
Dimethyl 2-(1-adamantylamino)-3-cyano-4-(2-
furyl)-4-oxo-2-butenephosphonate (VIb) was pre-
pared according to the general procedure from 1 g of
N-(1-adamantyl)(dimethyphosphono)ketenimine and
0.47 g of 2-furoylacetonitrile. H NMR spectrum
(CDCl3), δH, ppm: 1.69 m (6H, γ-CH2, adamant.), 2.08
m (6Н, α-СН2, adamant.), 2.16 m (3Н, β-СН,
3
ОСН2СН3, JHН 7.6 Hz), 9.53 br.s [1H, NHC(O)CH3].
13C NMR spectrum (DMSO-d6), δC, ppm: 14.07 and
14.40 (СН3СН2О), 22.70 (CH3C=O), 30.22 (СН,
1
1
adamant.), 32.56 d (СH2P, JPC 137.0 Hz), 36.38 (γ-
СН2, adamant.), 39.72 (α-СН2, adamant.), 53.27 d
2
(СН3ОР, JСP 5.8 Hz), 59.39 (C–N, adamant.), 61.19
2
2
(CH3CH2О), 61.64 [C(COOEt)2], 125.77 (С=N, JHP
adamant.), 3.48 d (2H, СН2Р, JHP 24.0 Hz), 3.83 d
2
3
12.4 Hz) and 132.46 (С=N, JHP 8.9 Hz), 153.53 and
(6Н, СН3ОP, JHP 11.2 Hz), 6.49 t (1Н, β'-СН, furan.,
31
3JHН 3.4 Hz), 6.82 t (1Н, β-СН, furan., JHН 3.4 Hz),
3
163.51 (С=О), 169.20 (CH3С=О). P NMR spectrum
7.55 d (1Н, α-СН, furan., 3JHH 3.4 Hz), 12.93 br.s (1H,
NH). 13C NMR spectrum (CDCl3), δC, ppm: 29.34
(DMSO-d6): δP 28.17 ppm.
Tetramethyl 2-tert-butylamino-1-cyano-1-propene-
phosphonate (VIIIa) was prepared according to the
general procedure from 1 g of N-tert-butyl(dimeth-
oxyphosphoryl)ketenimine and 0.73 g of dimethoxy-
phosphorylacetic acid nitrile. 1H NMR spectrum
(CDCl3), δH, ppm: 1.36 s [9H, С(CH3)3], 3.29 d (2H,
СН2Р, 2JHP 22.8, 4JHP 1.8 Hz), 3.65 d (6Н, СН3ОP, 3JHP
1
(СН, adamant.), 31.33 d (СH2P, JPC 134.9 Hz), 35.46
(γ-СН2, adamant.), 43.26 (α-СН2, adamant.), 53.39 d
(СН3ОР, JСP 6.3 Hz), 59.39 (C–N, adamant.), 80.74
[=C(CN)С(O)Fu, JСP 2.7 Hz], 111.76 (С≡N), 117.44
2
3
(β'-СН, furan.), 120.77 (β-CH, furan.), 145.52 (α'-CН,
2
furan.), 150.68 (α-С, furan.), 165.33 d (=СN, JСP
6.7 Hz), 177.25 (C=O). 31P NMR spectrum (CDCl3):
3
11.2 Hz), 3.75 d (6Н, СН3ОP, JHP 11.6 Hz), 9.26 br.s
(1H, NH). 13C NMR spectrum (CDCl3), δC, ppm: 30.85
δP 20.55 ppm.
1
3
[C(CH3)3], 31.14 d.d (СH2P, JCР 134.3, JСP 12.5 Hz),
Dimethyl 2-tert-butylimino-3-methylcarbox-
amido-3,3-diethoxycarbonylpropenephosphonate
(VIIa) was prepared according to the general proce-
dure from 1 g of N-tert-butyl(dimethoxyphosphoryl)-
ketenimine and 1.06 g of diethyl acetamidomalonate.
1H NMR spectrum (CDCl3), δH, ppm: 1.25 br.t (3H,
CH3CH2О, JHН 7.2 Hz), 1.42 s [9H, С(CH3)3], 2.07 s
(3H, CH3C=O), 2.73 d (2H, СН2Р, JHP 22.8 Hz), 3.82
d (6Н, СН3ОP, JHP 11.6 Hz), 4.12 br.q (2Н,
2
2
52.92 d (СН3ОР, JСP 5.3 Hz), 53.36 d (СН3ОР, JСP
1
5.9 Hz), 54.99 [C(CH3)3], 60.22 d. d (=CCN, JCР
199.8, 3JСP 5.6 Hz), 118.84 (С≡N, 2JCР 7.9 Hz), 166.89
t (=СN, 2JСP 6.2, 7.5 Hz). 31P NMR spectrum (CDCl3),
δP, ppm: 21.16 d (4JPP 7.4 Hz), 22.33 d (4JPP 7.4 Hz).
3
Tetramethyl 2-(1-adamantylamino)-1-cyano-1-
propenephosphonate (VIIIb) was prepared according
to the general procedure from 1 g of N-(1-adamantyl)-
2
3
3
ОСН2СН3, JHН 7.2 Hz), 9.46 br.s [1H, NHC(O)CH3].
(dimethyphosphono)ketenimine and 0.52
g
of
13C NMR spectrum (CDCl3), δC, ppm: 13.89 and 14.26
(СН3СН2О), 22.56 (CH3C=O), 27.99 [C(CH3)3], 30.53
d (СH2P, 1JPC 133.5 Hz), 53.36 d (СН3ОР, 2JСP 5.7 Hz),
57.31 [C(CH3)3], 60.38 (CH3CH2О), 60.85 [C(COOEt)2],
dimethoxyphosphorylacetic acid nitrile. 1H NMR spec-
trum (CDCl3), δH, ppm: 1.62 m (6H, γ-CH2, adamant.),
1.95 m (6Н, α-СН2, adamant.), 2.09 m (3Н, β-СН,
2
4
adamant.), 3.37 d (2H, СН2Р, JHP 23.2, JНР 1.9 Hz),
2
3
125.11 (С=N, JHP 12.2 Hz) and 131.32 (С=N,
3.74 d (6Н, СН3ОP, JHP 11.2 Hz), 3.80 d (6Н,
2JHP 10.2 Hz), 153.18 and 163.30 (С=О),
168.32 (CH3С=О).31P NMR spectrum (CDCl3): δP
29.09 ppm.
3
13
СН3ОP, JHP 11.6 Hz), 9.15 br.s (1H, NH). C NMR
spectrum (CDCl3), δC, ppm: 29.43 (СН, adamant.),
1
3
31.80 d. d (СH2P, JCР 134.9, JСP 11.7 Hz), 36.17 (γ-
СН2, adamant.), 43.44 (α-СН2, adamant.), 52.15 d
Dimethyl 2-(1-adamantylimino)-3-methylcarbox-
amido-3,3-diethoxycarbonylpropenephosphonate
(VIIb) was obtained according to the general proce-
2
2
(СН3ОР, JСP 4.2 Hz), 53.05 d (СН3ОР, JСP 5.6 Hz),
1
56.50 (C–N, adamant.), 60.24 d.d (=CCN, JCР 204.9,
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SVINTSITSKAYA et al.
2
3JСP 7.5 Hz), 119.14 (С≡N, JCР 6.7 Hz), 166.46 t
Dimethoxyphosphorylacetic acid N-(1-adamantyl)-
amide (Xb). H NMR spectrum (CDCl3), δH, ppm:
2
31
1
(=СN, JСP 6.8, 7.8 Hz). P NMR spectrum (CDCl3),
δP, ppm: 22.11 d (4JPP 4.8 Hz), 23.28 d (4JPP 4.8 Hz).
1.64 m (6H, γ-CH2, adamant.), 1.97 m (6Н, α-СН2,
adamant.), 2.05 m (3Н, β-СН, adamant.), 2.82 d (2H,
СН2Р, 2JHP 20.81 Hz), 3.77 d (6Н, СН3ОP, 3JHP 11.2 Hz),
6.39 br.s (1H, NH). 13C NMR spectrum (CDCl3), δC,
Dimethyl 2-(1,3-dimethyl-2,4,6-trioxohexahydro-
5-pyrimidinylidene)-2-tert-butilaminoethanephospho-
nate (IXa) was prepared according to the general
procedure from 1 g of N-tert-butyl(dimethoxyphos-
phoryl)ketenimine and 0.76 g of 1,3-dimethyl-
1
ppm: 29.21 (СН, adamant.), 35.14 d (СH2P, JPC
130.6 Hz), 36.12 (γ-СН2, adamant.), 40.98 (α-СН2,
adamant.), 52.44 (C–N, adamant.), 53.28 d (СН3ОР,
1
barbituric acid. H NMR spectrum (DMSO-d6), δH,
2
2JСP 4.7 Hz), 162.88 d (С=О, JСP 4.3 Hz). 31P NMR
2
ppm: 1.51 s [9H, С(CH3)3], 2.79 d (2H, СН2Р, JHP
spectrum (CDCl3): δP 25.63 ppm.
22.4 Hz), 3.17 s (6H, NCH3), 3.64 d (6Н, СН3ОP, 3JHP
11.2 Hz), 12.98 br.s (1H, NH). 13C NMR spectrum
(DMSO-d61), δC, ppm: 27.44 and 27.73 (NCH3), 30.34
d (СH2P, JPC 135.3 Hz), 30.37 [C(CH3)3], 52.76 d
Dimethoxyphosphorylacetonitrile. 1H NMR spec-
2
trum (CDCl3), δH, ppm: 2.89 d (2H, СН2Р, JHP
20.4 Hz), 3.81 d (6Н, СН3ОP, 3JHP 11.6 Hz). 13C NMR
2
1
(СН3ОР, JСP 6.3 Hz), 55.63 [C(CH3)3], 90.13
spectrum (CDCl3), δC, ppm: 14.99 d (СH2P, JPC
2
[=C(C=O)2], 150.56 [NС(O)N], 162.65 and 165.37
143.6 Hz), 53.96 d (СН3ОР, JСP 7.8 Hz), 112.79 d
[=C(C=O)2], 168.06 d (=СN, JСP 4.7 Hz). 31P NMR
2
2
(С≡N, JСP 4.6 Hz). 31P NMR spectrum (CDCl3): δP
spectrum (DMSO-d6): δP 22.88 ppm.
17.33 ppm.
Dimethyl 2-(1,3-dimethyl-2,4,6-trioxohexahydro-
5-pyrimidinylidene)-2-tricyclo[3.3.1.13,7]dec-1-yl-
aminoethanephosphonate (IXb) was prepared ac-
cording to the general procedure from 1 g of N-(1-
adamantyl)(dimethyphosphono)ketenimine and 0.55 g
REFERENCES
1. Leonov, A.A., Dogadina, A.V., Ionin, B.I., and Pet-
rov, A.A., Zh. Obshch. Khim., 1983, vol. 53, no. 1, p. 233.
1
2. Leonov, A.A., Komarov, V.Ya, Dogadina, A.V.,
Ionin, B.I., and Petrov, A.A., Zh. Obshch. Khim., 1985,
vol. 55, no. 1, p. 32.
of 1,3-dimethylbarbituric acid. H NMR spectrum
(DMSO-d6), δH, ppm: 1.69 m (6H, γ-CH2, adamant.),
1.97 m (6Н, α-СН2, adamant.), 2.11 m (3Н, β-СН,
2
adamant.), 2.74 d (2H, СН2Р, JHP 20.8 Hz), 3.27 s
3. Svintsitskaya, N.I., Dogadina, A.V., and Ionin, B.I., Zh.
Obshch. Khim., 2008, vol. 78, no. 11, p. 1795.
3
(6H, NCH3), 3.72 d (6Н, СН3ОP, JHP 11.2 Hz), 12.91
br.s (1H, NH). 13C NMR spectrum (DMSO-d6), δC,
ppm: 27.61 and 27.92 (NCH3), 29.53 (СН, adamant.),
4. Kram, D., Osnovy khimii karbanionov (Fundamentals of
Chemistry of Carbanions), Moscow: Mir, 1967.
1
31.21 d (СH2P, JPC 138.0 Hz), 35.69 (γ-СН2,
5. Reutov, O.A., Beletskaya, I.P., Butin, K.P., CH-Kisloty
adamant.), 43.28 (α-СН2, adamant.), 53.19 d (СН3ОР,
2JСP 6.0 Hz), 57.39 (C–N, adamant.), 90.73 [=C(C=O)2],
151.05 [NС(O)N], 163.15 and 166.17 [=C(C=O)2],
(CH-Acids), Moscow: Nauka, 1980.
6. Stevens, C.L., Freeman, R., and Noll, K., J. Org.
Chem., 1965, vol. 30, no. 11, p. 3718.
2
167.56 d (=СN, JСP 5.2 Hz). 31P NMR spectrum
(DMSO-d6): δP 22.93 ppm.
7. Titze, L., Aikher, T., Preparativnaya orgnicheskaya
khimiya (Preparative Organic Chemistry), Moscow:
Mir, 1999, p. 649.
8. Preparativnaya orgnicheskaya khimiya (Preparative
Organic Chemistry), Wul’fson, N.S., Ed., Moscow:
Khimiya, 1964.
9. Obshchii praktikum po organicheskoi khimii (General
Workshop on Organic Chemistry), Kosta, A.N., Ed.,
Moscow: Mir, 1965, p. 678.
Dimethoxyphosphorylacetic acid N-tert-butyl-
1
amide (Xa). H NMR spectrum (CDCl3), δH, ppm:
1.28 s [9H, С(CH3)3], 2.73 d (2H, СН2Р, 2JHP 21.2 Hz),
3.66 d (6Н, СН3ОP, 3JHP 11.6 Hz), 6.52 br.s (1H, NH).
13C NMR spectrum (CDCl3), δC, ppm: 28.20 [C(CH3)3],
34.84 d (СH2P, 1JPC 132.7 Hz), 51.20 [C(CH3)3], 52.79
2
2
d (СН3ОР, JСP 5.9 Hz), 163.08 d (С=О, JСP 4.6 Hz).
31P NMR spectrum (CDCl3): δP 25.30 ppm.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 4 2011