A new approach towards synthesis of phosphorylated alkenes

Article abstract of DOI:10.1134/S1070363215020024

New method of synthesis of trans-vinylphosphonates via reaction of trimethylsilyl(methyl)phosphonites with carbonyl compounds in the presence of carbon tetrachloride has been developed. The reaction involves formation of C-trimethylsilyl substituted ylide

Full text of DOI:10.1134/S1070363215020024

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 2, pp. 359–365. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © O.I. Kolodyazhnii, A.O. Kolodyazhnaya, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 2, pp. 185–191.
To the 80th Anniversary of B.I. Ionin
A New Approach Towards Synthesis of Phosphorylated Alkenes
O. I. Kolodyazhnii and A. O. Kolodyazhnaya
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 1, Kiev, 02094 Ukraine
e-mail: olegkol321@rambler.ru
Received November 6, 2014
Abstract—New method of synthesis of trans-vinylphosphonates via reaction of trimethylsilyl(methyl)phos-
phonites with carbonyl compounds in the presence of carbon tetrachloride has been developed. The reaction
5
involves formation of C-trimethylsilyl substituted ylides and 2-chloro-1,2λ -oxaphosphetanes as intermediates.
Keywords: C-silylated tertiary phosphine, vinylphosphonate, diene phosphonate, C-trimethylsilyl substituted
5
ylide, 1,2λ -oxaphosphetane
DOI: 10.1134/S1070363215020024
Phosphonic acids have been recognized as isosteres
of some biologically important phosphates such as
nucleotides, phospholipids, and polyphosphates of
nucleosides and carbohydrate-containing phosphates
phosphonates serve as monomers leading to non-
inflammable phosphorus-containing polymers [18, 19]
and are thus applied as fire-retardants [20–22].
In view of the above, development of new ap-
proaches to prepare phosphonates and vinylphospho-
nates is of definite interest. In this work we describe a
convenient method of vinylphosphonates synthesis; the
procedure is based on the reaction of C-trimethylsilyl-
[1–4]; they also exhibit biological activity as
regulators, mediators, or inhibitors of enzymes [1].
Moreover, phosphonates have been applied in general
organic synthesis as the Horner–Emmons reagents in
the reactions with aldehydes and ketones yielding
olefins [2].
(
methyl)phosphonates with easily accessible carbonyl
compounds and carbon tetrachloride. Subsequent
reduction of the prepared vinylphosphonates can yield
alkylphosphonates. The approach may be considered
as a new method of modification and extension of
alkyl chain of tertiary phosphines and phosphonates
Substituted vinylphosphonates are of interest as
building blocks in the synthesis of anticancer and
antiviral agents [3–5], immunosuppressants, various
metabolites [6–11], and insecticides as well as
antibacterial and antifungal drugs. Vinylphosphonates
are used as substrates of the Michael reaction to give
aziridine phosphonates, aminophosphonates, and
aminophosphonic acids derivatives [12–17]. Vinyl-
(
Scheme 1).
Reaction of trimethylsilylphosphonates I with
carbonyl compounds and CCl was performed via
4
stirring of equimolar amounts of the reagents in diethyl
Scheme 1.
R1
R1
R1
O
O
R1
R1
2
CCl /R CH=O
P
H2
P
H
4
H
P
CH SiMe
R1
2
3
_
Me SiX
Pd/C
H
H
3
R2
H
H
R2
I
II
III
1
2
R = Alk, AlkO, Et N; R = Ar, Alk, AlkCH=CH.
2
3
59

3
60
KOLODYAZHNII, KOLODYAZHNAYA
Scheme 2.
R
R
O
XC H CH=O
6
4
R
R
CCl4
P
H
P
CH SiMe
2
3
H
C H X
6
4
Ia−Ic
IIa−IIf
R = ОEt (Ia), Оi-Pr (Ib), Et
2
N (Ic); R = Et
2
N, X = Ph (IIa); R = OEt, X = Ph (IIb); R = Oi-Pr, X = Ph (IIc); R = OEt, X =
O
2
6
-BrC H
4
(IId); R = Et
2
N, X = 2-FC
6
H
4
2
(IIe); R = Et N, X =
(IIf).
O
Scheme 3.
H
H
H
R PCH SiMe
2
2
3
O
R
O
CCl4
P
R
H
H
H
IV
R = EtO, Et N.
2
Scheme 4.
H
O
Et N
2
1
: 1
Et N
P
H
2
CHO
CHO
(
E)-V
O
(
Et N) PCH SiMe
2 2 2 3
CCl4
H
O
H
P NEt2
Et N
NEt2
2
1
: 2
Et N
P
H
2
O
(E,E)-VI
ether or in bulk during few hours. The reaction
firmed by comparison of their physical and chemical
parameters with those for the reference vinylphos-
phonates prepared via other methods.
3
1
progress was monitored via TLC or P NMR spec-
troscopy. The target olefins IIa–IIf were isolated by
column chromatography in 60–82% yield. According
3
1
to the P NMR spectroscopy data, the reactions
proceeded stereoselectively with formation of of trans-
vinylphosphonates IIa–IIf (Scheme 2).
The reaction with unsaturated aldehydes gave diene
phosphonates IVa and IVb. Strong absorption at 1560
–
1
and 1620 cm was observed in IR spectrum of diene
IVa, assigned to asymmetric and symmetric stretching
of the transoid bonds; the absorption bands at 3010,
Configuration of the olefins IIa–IIf was elucidated
1
from NMR spectroscopy data. In particular, in the H
–
1
3
030, 3090–3100, and 930–940 cm (stretching and
NMR spectra two doublets of doublets of the olefinic
protons were observed at 6–8 ppm with spin-spin
out-of-plane deformations of unsubstituted vinyl
group) were also observed. A group of signals was
3
2
coupling constants J
17 and J 19 Hz, cor-
HH
PH
1
responding to the trans-location of hydrogen atoms
with respect to the double bond. Structures of
vinylphosphonates IIb–IId were additionally con-
observed at 6–8 ppm in the H NMR spectrum, the
integral intensity corresponding to four protons of the
diene system (Scheme 3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

A NEW APPROACH TOWARDS SYNTHESIS OF PHOSPHORYLATED ALKENES
361
Scheme 5.
Catalytic hydrogenation of the vinylphosphonates
with hydrogen at low pressure over Pd/C gave
alkylphosphonates VII and VIII (Scheme 5).
EtO
EtO
O
EtO
EtO
O
P
H
P
H
H2
Mechanism of the vinylphosphonates IIa–IIf forma-
tion coincided with the results of our previous studies
H
H
Pd/C
H
Ar
H
Ar
[23–27]. The tertiary phosphine reacted with carbon
II
VII, VIII
tetrachloride at the first stage to give P-chloro ylide
IV; the product further reacted with the carbonyl
5
The reactions with aldehydes proceeded
regioselectively. In particular, depending on the ratio
of the reagents, the reaction of trimethylsilylphos-
phonate Ic with terephthalic aldehyde occurred with
sequential substitution of one or two carbonyl groups
leading to formation of (phosphonovinyl)benzaldehyde
V and bis(vinylphosphono)benzene VI. The reaction
was performed at 20°С in THF (Scheme 4).
compound to form 1,2λ -oxaphosphetane V. The latter
is the P-chlorine-containing analog of the Wittig reac-
tion intermediate; however, due to its special structural
features it decomposed with elimination of trimethyl-
silyl chloride to yield vinylphosphonate instead of
tertiary phosphine oxide and alkene formation
(Scheme 6).
Formation of C-silyl substituted P-chloro ylides IV
was confirmed with H,
spectroscopy. The doublet signal of the P=CH group
proton was observed at 0 to –5 ppm, JPH 7–8 Hz; the
ylide carbon atom resonated as doublet at 30 ppm ( JРС
100–120 Hz), confirming carbanion character of the
1
13
31
Compounds V and VI were stable and readily
crystallized from nonpolar solvents. The results of
elemental analysis and spectroscopy study of
compounds V and VI coincided with their structure. In
particular, IR spectrum of compound V contained
C, and
P NMR
2
1
–
1
–1
absorption bands at 2700 cm (CH) and 1690 cm
C=O), pointing at appearance of aldehyde group;
atom. Chemical shift δ of the P-chloro ylides IV was
P
(
of 70–90 ppm, corresponding to the “onium” nature of
the phosphorus atom. 2-Chloro-1,2λ -oxaphosphetanes
–
1
5
other characteristic bands at 1550 cm (C=C) as well
as at 1205 and 1215 cm (P=O) were observed in the
–
1
V, unstable four-membered intermediates formed at
the second stage of the reaction, were registered by
spectroscopy techniques only in the case of the
reaction of tertiary phosphines I with trifluoroaceto-
phenone. As we demonstrated earlier, the electron-
spectrum. IR spectrum of compound VI contained
–
1
absorption bands at 1560 (C=C) and 1200 cm (P=O).
1
In H NMR spectrum of compound V, a singlet signal
assigned to aldehyde group was observed at 11.5 ppm.
Two doublets of doublets assigned to vinyl protons
were found at 6.5 (PCH=C) and 7.7 ppm (PC=CH), the
3
acceptor bulky trifluoromethyl group at C atom of
oxaphosphetane increased its stability; hence, such
oxaphosphetanes could be detected by physico-
chemical methods and in certain cases even isolated
3
3
spin-spin coupling constants being of J 17.0, J
1
HH
PH
2
9.0, and JPH 17.5 Hz; the spectral data thus
5
confirmed the trans-location of hydrogen atoms with
respect to the C=C bond. Doublet of doublets of the
ortho-protons of unsymmetrically 1,4-disubstituted
[27]. 2-Chloro-1,2λ -oxaphosphetane X containing
3
CF
and Ph substituents at C atom was a transparent
3
oily substance. At room temperature compound X was
gradually converted into alkenephosphonate XI with
elimination of trimethylsilyl chloride. Heating in-
creased the conversion rate, and the oxaphosphetane
was completely transformed into alkenephosphonate
1
aromatic ring was also observed. In H NMR spectrum
of compound VI, the protons of the aromatic ring
resonated as finely resolved singlet, coinciding with
high symmetry of the molecule.
Scheme 6.
R2
R1
R1
O
O
R2
H
H
H
P
2
R1
CCl4
R CH=O
1
2
1
P+
R PCH SiMe
R P=CHSiMe
2
3
2
3
_Me
SiCl
3
R1
SiMe3
Cl
_
H
Cl
IV
V
II
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

3
62
KOLODYAZHNII, KOLODYAZHNAYA
Scheme 7.
R2
O
R1
R1
Ph
R1
Ph
H
PCH SiMe3
2
R1
R1
P
CF3
to
R1
SiMe3
CF3
Ph
P
Cl
_
CCl4
Me SiCl
3
Xa
O
O
H
R1
2
R = CF3
XIа, XIb
R1 P=CHSiMe3
R2
HO
Ph
CF
H
Cl
O
O
R1
R1
IXа, IXb
H O
3
2
Ph
H
_
R1
Cl
P
P+
SiMe3
XIIа
R1
SiMe3
Xb
1
2
1
2
R = i-PrO, R = CF (a); R = Et N, R = CF (b).
3
2
3
XI that was isolated in good yield via vacuum
distillation. The other 2-chlorooxaphosphetanes (not
containing CF3 group) were converted into the
vinylphosphonates even below 0°C, but in some cases
equilibrium ratio of the covalent and ionic forms
Xa ↔ Xb. The downfield shifted δ values observed in
P
the case of chloroform solutions indicated significant
degree of ionization of the P–Cl bond and the
tetracoordinated nature of the phosphorus atom.
3
1
their formation was registered in P NMR spectra. For
1
5
example, formation of oxaphosphetane X with R =
Possibility of 2-chloro-1,2λ -oxaphosphetanes disso-
2
i-PrO and R = H was confirmed by observation of the
ciation via the P–Cl bond has been discussed earlier in
[27] (Scheme 7).
signal at 40 ppm which gradually vanished with
appearance of another signal at 15 ppm, assigned to
diisopropyl 2-styryl phosphonate IIc; the latter was
isolated and characterized. Oxaphosphetane X was
easily hydrolyzed to yield crystalline 2-trifluoro-
methyl-2-hydroxy(ethyl)phosphonate XI; compound X
was converted into the corresponding vinylphospho-
nate II upon heating at 40°С or after prolonged
incubation at room temperature. Hydrolysis of oxa-
phosphetane X in the presence of trimethylamine
To conclude, the reaction of trimethylsilyl(methyl)-
phosphonates with aldehydes in the presence of CCl is
4
a convenient approach to stereoselective synthesis of
phosphorus-containing olefins, suitable for application
in fine organic synthesis.
EXPERIMENTAL
NMR spectra were recorded with a Varіan VXR-
yielded 2-hydroxy(alkyl)phosphonate XII. Structure of
1
13
3
1
00 spectrometer at 300 MHz ( H), 60 MHz ( C),
5
2
-chloro-1,2λ -oxaphosphetane X was confirmed by
31
19
26.16 MHz( P), or 225.8 MHz ( F) referenced to
NMR spectroscopy: the signals of trimethylsilyl group
1
13
31
19
Me Si ( H and C), 85% H PO ( P), or CFCl ( F).
3
2
4
3
4
3
at 0.2 ppm, C H protons at 2.0 ppm ( J 18.0 Hz), and
PH
The chemicals, silica gel, and TLC plates (Polіgram
SIL G/UV254) from Fluka and Acros suppliers were
used. The solvents were distilled before use. The
starting trimethylsilyl(methyl)phosphonates Ia–Ic were
synthesized as described elsewhere [24].
4
1
C H at 4.5 ppm were observed in the H NMR
spectrum. P chemical shift of compound X was of
8.0 ppm, typical of the phosphonium atom in four-
3
1
4
membered phosphetane ring.
The δP value in oxaphosphetanes X spectra
depended on the solvent polarity. Upfield shift of the
signals (≈30 ppm) in less polar solvents (hexane or
Bis(diethylamido) (E)-styrylphosphonate (IIa).
Carbon tetrachloride (2 mL) (or 0.012 mol of bromo-
trichloromethane) was added to a solution of 0.01 mol
of tetraethyldiaminotrimethylsilyl(methyl)phosphine Ic
at –70°C. The reaction mixture was allowed to warm
up to 0°C and was stirred during 15 min. After
addition of benzaldehyde (0.015 mol), the reaction
CCl ) was observed, whereas in more polar solvents
4
(
chloroform or acetonitrile) downfield shift of the
signals occurred (up to 50 ppm); that was possibly due
to the P–Cl bond dissociation and the change of the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

A NEW APPROACH TOWARDS SYNTHESIS OF PHOSPHORYLATED ALKENES
363
mixture was stirred during 14 h at room temperature.
Then the solvent was removed, and the residue was
kept in vacuum (0.05 mmHg) at 100°C during 15 min
in order to remove excess of benzaldehyde; then the
residue was recrystallized from hexane. Yield 80%
Bis(diethylamido)-(E)-2-(o-fluorophenyl)ethenyl-
phosphonate (IIe) was prepared similarly. Yield 60%,
bp 130°С (0.1 mmHg), mp 114°С. Н NMR spectrum
1
3
(СDС1 ), δ, ppm: 1.08 t (6H, CH , J 7.0 Hz), 3.08
3
3
HH
3
m (4H, CH O, J 7.5 Hz), 6.25 d.d (1H, PCH=C,
2
HH
3
2
(
1
(
7
75% in the case of bromotrichloromethane), mp
JHH 17.5, J 17.0 Hz), 7.03 m (2H, C H ), 7.40 d.d
HP 6 4
1
3
3
03.5°C. H NMR spectrum (CDCl ), δ, ppm: 1.38 t
(1H, PC=CH, J 17.5, J 18.0 Hz), 7.46 d (2H, C H ,
HP 6 4
3
3
3
3
13
12Н, СН СН , J 7.0 Hz), 1.38 d.q (8H, CH N, J
.0, J 11.0 Hz), 6.60 d.d (1Н, РСН=С, J 17.2,
J 8.5 Hz). C NMR spectrum (C D ), δ , ppm: 13.77,
3
2
НН
2
НН
6 6 С
3
3
2
37.90, 114.50, 118.10 d (P–CH=C, J 152.0 Hz),
128.70, 131.66 d (PC=С, J 24.0 Hz), 144.17, 161.90
РН
HH
PC
3
3
2
JPH 18.0 Hz), 7.75 d.d (1Н, С=СН, J 17.5, J
1
(
1
1
НН
РН
РС
1
3
2
31
9 Hz), 7.65 m (5Н, С Н ). C NMR spectrum
C D ), δ , ppm: 13.70, 41.85, 114.50 d (PCH=C, J
52.0 Hz), 128.70, 131.66 d (РC=С, J 24.0 Hz),
PC
44.17, 161.90 d ( J 30.0 Hz). Р NMR spectrum
d ( J 247.5 Hz). Р NMR spectrum (CDCl ): δ
6
5
CF 3 P
1
19.06 ppm. Found, %: C 61.81; H 8.42; P 9.61.
C H FN OP. Calculated, %:C 61.52; H 8.39; P 9.92.
6
6
С
PC
2
16 26
2
3
31
PC
Bis(diethylamido)-(E)-2-(1,3-benzodioxol-5-yl)-
vinylphosphonate (IIf) was prepared similarly. Yield
(
CDCl ): δ 24.50 ppm.
3 P
1
Diethyl (E)-styrylphosphonate (IIb) was prepared
similarly. Yield 60%, mp 122°С (0.06 mmHg) [28–
60%, bp 115–135°С (0.1 mmHg). Н NMR spectrum
3
(CDCl ), δ, ppm: 1.08 t (12Н, CH , J 7.0 Hz), 3.07
3
3
НН
1
3
0]. Н NMR spectrum (СDС1 ), δ, ppm: 1.28 t (3H,
m (4Н, CH N), 5.96 s (2Н, OCH O), 6.14 d.d (1Н,
3
2
2
3
3
3
2
JHH 7.0 Hz), 1.30 t (3H, CH , J 7.0 Hz), 4.15 d.q
4H, OCH , J 7.0, J 11.0 Hz), 6.30 d.d (1H,
CH=С, J 17.2, J 17.2 Hz), 7.10 d.d (1H, С=CH,
JHH 17.2, J 22.0 Hz), 7.10–7.40 m (5H, C H ). C
NMR spectrum (CDCl ), δ , ppm: 16.30, 61.6 d ( J
.0 Hz), 110.70 d (CH, J 190.0 Hz), 128.00, 129.00,
31.10, 136.10, 149.20 d (CH, JPС 6.1 Hz). Р NMR
РCH=C, J 17.0, J 17.5 Hz), 6.78–7.32 m (6Н,
НН РН
3
HH
3
3
13
(
РC=CН, C H ). C NMR spectrum (CDCl ), δ , ppm:
2
HH
PH
6 5 3 С
3
2
13.86, 38.00, 100.94, 105.63, 107.97, 115.39, 116.63,
HH
3
PH
3
13
31
122.69, 129.93, 130.03, 145.00, 147.76, 148.32.
Р
PH
6
5
2
NMR spectrum (CDCl ): δ 24.00 ppm. Found, %: C
3
1
С
PС
3
P
6
1
60.66; H 8.21; P 9.05. C H N O P. Calculated, %: C
17 27 2 3
60.34; H 8.04; P 9.15.
PС
2
31
spectrum (CDCl ): δ 18.00 ppm.
3
P
Bis(diethylamido)-4-phenyl-(1E,3E)-1,3-butadi-
enylphosphonic acid (IV). Carbon tetrachloride
(0.03 mol) was added to a solution of 0.02 mol of
diethylaminotrimethylsilyl methylphosphonite Ic in
10 mL of diethyl ether at –70°C followed by increas-
ing of temperature to 0–5°С and stirring of the reaction
mixture for 15 min. Then cinnamaldehyde (0.02 mol)
was added, and the reaction mixture was incubated
Diisopropyl (E)-styrylphosphonate (IIc) was
prepared similarly. Yield 60%, bp 122°С (0.06 mmHg)
1
[
(
28]. Н NMR spectrum (СDС1 ), δ, ppm: 1.24 d.d
3
3
3
12Н, СН С, J
ОСН), 6.10 d.d (1Н, PCH=C, J 17.5, J 18.0 Hz),
.70 d.d (1Н, PС=СН, J 17.5, J 19.0 Hz), 7.10 m
5Н, С Н ). C NMR spectrum (C D ), δ , ppm:
6.0, J 2.5 Hz), 4.33 m (2Н,
3
HH
PH
3
2
HH
PH
3
3
7
(
2
(
HH PH
1
3
6 5 6 6 С
2
3.60, 23.80, 70.21 d (OCH, J 6.0 Hz), 120.80 d
during 18 h at room temperature. Yield 70%, bp 170–
PС
1
1
CH, J 180.0 Hz), 128.35, 129.00, 131.10, 136.10,
175°С (0.06 mmHg). Н NMR spectrum (CDCl ), δ,
PС
3
2
31
3
1
49.20 d (CH, JPС 6.1 Hz). Р NMR spectrum
ppm: 1.4 t (12H, CH , J 7.0), 3.30 d.q (8H, CH N,
3
НН
2
3
(
CDCl ): δ 16.00 ppm.
JPH 10.0 Hz), 6.30 m and 7.30 m (4Н, СН=СН), 7.80
m (5Н, C Н ). Р NMR spectrum (CDCl ): δ 23.30
3
P
3
1
6
5
3
P
Diethyl (E)-2-bromostyrylphosphonate (IId) was
prepared similarly. Yield 75%, mp 82°C (mp 82°С
ppm. Found, %: C 67.77; H 9.20; Р 9.66. С Н N ОР.
1
8
29
2
1
Calculated, %: C 67.47; H 9.12; P 9.67.
[
31]). Н NMR spectrum (СDС1 ), δ, ppm: 1.29 t (6H,
3
3
3
CH , J 7.0 Hz), 4.07 m (4H, CH O, J 7.5 Hz),
Bis(diethylamido)-4-formylphenyl-(E)-vinylphos-
phonic acid (V) was prepared similarly from 0.02 mol
of diethylaminotrimethylsilyl methylphosphonite Ic,
0.03 mol of carbon tetrachloride, and 0.02 mol of
terephthalic aldehyde. After removal of the solvent, the
residue was recrystallized from diethyl ether–pentane
3
НН
2
НН
3
2
6
(
1
.18 d.d (1H, PCH=C, J 17.5, J 17.0 Hz), 7.30 d
HH PН
3
3
2H, C H , J 8.5 Hz), 7.37 d.d (1H, PC=CH, J
6 4 НН НН
3
3
7.5, J 18.2 Hz), 7.46 d (2H, o-BrC H , J 8.5
PН 6 4 НН
1
3
Hz). C NMR spectrum (C D ), δ , ppm: 16.40 d
6
6
С
2
2
(
CH , J 7.0 Hz), 61.90 d (CH O, J 5.6 Hz),
3 PC 2 PC
2
1
1
1
6
14.80 d (PC=C, J 192.0 Hz), 124.40, 128.50,
32.60, 133.70 d ( J 24.0 Hz), 147.30 d (PC=C, J
.9 Hz). Р NMR spectrum (CDCl ): δ 19.06 ppm.
mixture. Yield 50%, mp 92.5–94°С. Н NMR spec-
РС
3
2
3
trum (CDCl ), δ, ppm: 1.40 t (12Н, СН СН, J
РС
PC
3
3
НН
3
1
3
3
7.0 Hz), 3.41 d.d (8Н, СН N, JНН 7.0, JPH 10.5 Hz),
3
P
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

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64
KOLODYAZHNII, KOLODYAZHNAYA
2
8
.10 d.d (4Н, С Н ), 6.80 d.d (1Н, РСН=С, J 17.5,
added dropwise to a solution of diisopropyl trimethyl-
6
4
HH
2
3
3
JРН 17.5 Hz), 7.85 d.d (1Н, С=СН, J 17.5, J
silyl(methyl)phosphonite [32] (0.02 mol) in 20 mL of
diethyl ether at stirring and cooling to –70°С. Then
temperature was increased to ambient, the reaction
mixture was stirred during 3 h, and the solvent was
НН
PH
4
1
1
9.0 Hz), 8.00 d and 8.10 d (4Н, С Н , J 9.0 Hz),
6 4 HH
1
3
0.30 s [1Н, С(О)Н]. C NMR spectrum (CDCl ), δ ,
ppm: 14.01, 41.7 d (J 6.0 Hz), 105.2 d (РС, J
60.0 Hz), 130.1, 131.5, 136.0, 142.5, 154.2 d ( J
2.0 Hz), 191.5. Р NMR spectrum (CDCl ): δ 23.7 ppm.
3
C
2
РС
3
1
1
3
evaporated. Yield 80%, bp 65°С (0.06 mmHg). Н
РС
31
NMR spectrum (CDCl ), δ, ppm: 0.01 d (9Н, CH Si,
3
P
3
3
4
3
Found, %: С 63.13; Н 8.41; Р 9.52. С Н N O Р.
JPH 0.3 Hz), 0.48 d (1Н, Р=СН, J 3.0 Hz), 1.25 d.d
(6Н, (СН ) СH, JPH 3.0 Hz), 4.62 m (2Н, ОСН). C
3 2
1
7
27
2
2
PH
3
13
Calculated, %: С 63.34; Н 8.44; Р 9.61.
3
NMR spectrum (C D ), δ , ppm: 0.89 d (CH Si, J
6
6
С
3
PC
Bis[(1E,1'E)-2-tetraethyldiamidophosphono-
vinyl]benzene (VI) was prepared similarly from
.02 mol of diethylaminotrimethylsilyl methylphosphonite
Ic, 0.03 mol of carbon tetrachloride, and 0.01 mol of
terephthalic aldehyde. After removal of the solvent, the
residue was recrystallized from pentane. Yield 50%,
1
6
.0 Hz), 15.00 d (Р=С, J 155.0 Hz), 21.30 d (СН С,
PC 3
3
2
31
JPC 6.0 Hz), 71.55 d (ОСН, J 9.0 Hz). Р NMR
PC
0
spectrum (CDCl ): δ 59.00 ppm.
3
P
Bis(diethylamido)-3,3,3-trifluoro-2-phenylpro-
penephosponate (IXb) was prepared similarly. Yield
1
1
7
(
0%, bp 150°С (0.07 mmHg). Н NMR spectrum
yellow crystals, mp 188.5–190°С. Н NMR spectrum
3
3
CDCl ), δ, ppm: 1.38 t (12H, CH , J 7.0 Hz), 3.27
(
3
(
CDCl ), δ, ppm: 1.05 t (24H, СН СН, J 7.0 Hz),
3 3 НН
3
3
НН
3
3
3
d.q (8H, CH N, J 10.0 Hz), 6.80 d.q (1Н, С=СН,
JPH 12.0, J 1.5 Hz), 7.60 m (5Н, C Н ). F NMR
spectrum (CDCl ): δ –68.11 ppm. Р NMR spectrum
.03 d.q (16Н, NСН , J 7.0, J 11.0 Hz), 6.33 d.d
2Н, РСН=С, J 17.0, J 17.0 Hz), 7.30 d.d (2Н,
С=СН, J 17.0, J 19.0 Hz), 7.44 m (4Н, С Н ).
C NMR spectrum (CDCl ), δ , ppm: 14.00 d ( J
.0 Hz), 41.80 d ( J 6.0 Hz), 105.70 d (PCH=, J
80.0 Hz), 129.80, 137.70, 154.20 d ( JPC 32.0 Hz). Р
2
PH
2
НН
PH
2
4
19
3
2
HF
6
5
НН
PH
3
1
3
3
3
F
НН
РН
6
4
1
3
3
(
CDCl ): δ 23.50, 16.20 ppm. Found, %: C 56.35; H
3 P
3
С
PC
2
1
7
.23; P 8.55. C H F N OP. Calculated, %: C 56.35;
17 26 3 2
8
1
PC
PC
31
2
H 7.23; P 8.55.
NMR spectrum (CDCl ): δ 24.80 ppm. Found, %: С
3
P
2-Chloro-2,2-diisopropoxy-2,2-dihydro-4-phenyl-
4-trifluoromethyl-3-trimethylsilyl-1,2λ -oxaphos-
5
6
1.31; Н 9.66; N 10.85. С Н Н О Р . Calculated, %:
20 48 2 2 2
С 61.16; Н 9.47; N 10.97.
phetane (X). Carbon tetrachloride (0.04 mol) was
added dropwise to a solution of 0.02 mol of diiso-
propyl trimethylsilyl(methyl)phosphonate in 20 mL of
diethyl ether at stirring and cooling to –70°С. Then
temperature was increased to ambient, and the reaction
mixture was stirred during 2–3 h; the reaction progress
Diethyl (E)-(2-bromophenylethyl)phosphonate
VII). A solution of 120 mg of vinylphosphonate II in
(
1
1
0 mL of ethanol was subject to hydrogenation over
0% Pd/C (20 mg) at atmospheric pressure. The
mixture was vigorously stirred at room temperature for
3
1
was monitored by P NMR spectroscopy. Then
0.025 mol of 2,2,2-trifluoroacetophenone was added
and the mixture was stirred during 2–4 h, and the
3
1
h, and the catalyst and solvent were removed. Yield
1
20 mg (99%), colorless oily substance. Н NMR
3
spectrum (CDCl ), δ, ppm: 1.30 t (6H, J 7.1 Hz),
3
HH
solvent was evaporated in vacuum. Yield 90%, oily
2
.10 m (2H, CH ), 2.91 m (2H, CH ), 4.04–4.10 m
2 2
1
3
1
unstable substance. Н NMR spectrum (CDCl ), δ,
3
(
4H, CH O), 7.16–7.30 m (4H, C H ). Р NMR
2 6 5
3
ppm: 0.20 s (9Н, CH Si), 0.90 d (12Н, СН С, J
.0 Hz), 1.95 d (1Н, РСН, J 18.0 Hz), 4.20 m (2Н,
ОСН), 7.30 m and 7.80 m (5Н, С Н ). F NMR
3
3
НН
spectrum (CDCl ): δ 32.00 ppm. Found, %: C 44.88;
3
P
2
6
РН
H 5.65; P 9.64. C H BrO P. Calculated, %: C 44.88;
1
2
18
3
1
9
6
5
H 5.65; P 9.64.
3
1
spectrum (CDCl ): δ –68.40 ppm. Р NMR spectrum
3
F
Diethyl (E)-(2-phenylethyl)phosphonate (VIII)
was prepared similarly from compound IIb. Yield
(
CDCl ): δ 48.0 ppm.
3 P
1
3
Diisopropyl 2-phenyl-3,3,3-trifluoroprop-1-enyl-
-phosphonate (XIa). Oxaphosphetane X was heated
9
7
(
0%. Н NMR (CDCl ), δ, ppm: 1.32 t (6H, CH , J
3 3 PH
1
.1 Hz), 2.11 m (2H, CH ), 2.85 m (2H, CH ), 4.09 q
4H, OCH , J 7.4 Hz), 7.21–7.29 m (5H, C H ). Р
2
2
3
31
at 60°C during 0.5 h and distilled in vacuum. Yield
2 HH 6 5
1
7
7% (Е : Z = 7 : 1), bp 115°С (0.07 mmHg). Н NMR
NMR spectrum (CDCl ): δ 32.00 ppm. Found, %: C
3
P
spectrum (CDCl ), δ, ppm: Е-isomer, 1.03 d (6Н,
3
5
5
9.50; H 7.91; P 12.79. C H O P. Calculated, %: C
12 19 3
3
3
СН С, J 6.4 Hz), 1.12 d (6Н, СН С, J 6.2 Hz),
.45 m (2Н, ОСН), 6.44 d.q (1Н, PСН=С, J 1.5,
3
HH
3
HH
9.50; H 7.91; P 12.79.
Diisopropoxychlorophosphonium (trimethylsilyl)-
methylide (IXa). Carbon tetrachloride (0.04 mol) was
4
4
FH
2
JPC 12.0 Hz), 7.30 m (5Н, С Н ); Z-isomer, 1.28 d
6
5
3
3
(6Н, СН С, J 6.5 Hz), 1.32 d (6Н, СН С, J 6.0 Hz),
3
HH
3
HH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015

A NEW APPROACH TOWARDS SYNTHESIS OF PHOSPHORYLATED ALKENES
365
2
4
7
9
9
9
.75 m (2Н, ОСН), 6.20 d (1Н, С=СН, J 8.8 Hz),
S0040-4020(97)00814-4.
PH
3
1
.30 m (5Н, С Н ). Р NMR spectrum (CDCl ): δP
.30 (Е), 7.68 (Z) ppm. Found, %: C 53.57; H 5.99; P
.21. C H F O P. Calculated, %: C 53.57; H 5.99; P
13. Robiette, R., Defacqz, N., Stofferis, J., and Marchand-
Brynaert, J., Tetrahedron, 2003, vol. 59, no. 23, p. 4167.
DOI: 10.1016/S0040-4020(03)00580-5.
6
5
3
1
5
20
3
3
1
4. Arimori, S., Kouno, R., Okauchi, T., and Minami, T.,
.21.
J. Org. Chem., 2002, vol. 67, no. 21, p. 7303. DOI:
Diisopropyl 1-(trimethylsilyl-2-hydroxyphenyl-
,3,3-trifluoro)propylphosphonate (XIIa). Yield
0%, bp 118°С (0.04 mmHg). Н NMR spectrum
CDCl ), δ, ppm: 0.5 s (9Н, CH Si), 0.92 m (12Н,
СН С), 2.87 d (1Н, РСН, J 20.0 Hz), 4.48 m and
.85 m (3Н, СНO, ОН), 7.17–7.51 m (5Н, С Н ). Р
NMR spectrum (CDCl ): δ 18.70 ppm. F NMR
spectrum (CDCl ): δ –77.60 ppm. Found, %: С 49.97;
1
0.1021/jo020403c.
3
8
(
1
5. Yokomatsu, T., Yamagishi, T., Suemune, K., Yoshida, Y.,
and Shibuya, S., Tetrahedron, 1998, vol. 54, no. 5,
p. 767. DOI: 10.1016/S0040-4020(97)10341-6.
1
3
3
2
3
РН
16. Kim, D.Y., and Rhie, D.Y., Tetrahedron, 1997, vol. 53,
31
4
no. 40, p. 13603. DOI: 10.1016/S0040-4020(97)00880-6.
6
9
5
1
3
P
17. Junker, H.-D. and Fessner, W.-D., Tetrahedron Lett.,
1998, vol. 39, no. 3, p. 269. DOI: 10.1016/S0040-4039
(97)10498-1.
3
F
H 6.89. C H F O P. Calculated, %: С 50.69; H 7.09.
18
30
3
4
1
8. Jin, S. and Gonsalves, K.E., Macromolecules, 1998,
REFERENCES
vol. 31, no. 4, p. 1010. DOI: 10.1021/ma9707289.
1
2
9. UK Patent 2102427, 1983; C. A., 1983, vol. 99, p. 88368d.
0. Jin, J.I., US Patent 4031054, 1977; C. A., 1977, vol. 87,
1
2
3
4
. Giordano, C. and Castaldi, G., J. Org. Chem., 1989,
vol. 54, no. 6, p. 1470. DOI: 10.1021/jo00267a050.
. Maryanoff, B.E. and Reitz, A.B., Chem. Rev., 1989,
vol. 89, no. 4, p. 863. DOI: 10.1021/cr00094a007.
. Minami, T. and Motoyoshiya, J., Synthesis, 1992, no. 4,
p. 333. DOI: 10.1055/s-1992-26103.
. Stowasser, B., Budt, K.-H., Jian-Qi, L., Peyman, A., and
Ruppert, D., Tetrahedron Lett., 1992, vol. 33, no. 44,
p. 6625. DOI: 10.1016/S0040-4039(00)61002-X.
. Hirschmann, R., Smith, A.B., Taylor, C.M., Benkovic, P.A.,
Taylor, S.D., Yager, K.M., Sprengeler, P.A., and Ben-
kovic, S.J., Science, 1994, vol. 265, no. 5169, p. 234.
DOI: 10.1126/science.8023141.
. Graeve, R., Thorwart, W., Raiss, R., Weithmann, K.U.,
and Mullner, S., US Patent 5627173, 1997.
. Lennon, P.J., US Patent 5434288, 1995.
p. 54500.
2
2
1. Joseph, P. and Tretsiakova-McNally, S., ACS Sym-
posium Series, 2012, vol. 1118, ch. 13, p. 37. DOI:
10.1021/bk-2012-1118.ch003.
2. Howell, B.A. and Dumitrascu, A., ACS Symposium
Series, 2012, vol. 1118, ch. 17, p. 235. DOI: 10.1021/
bk-2012-1118.ch017.
2
2
3. Kolodiazhnyi O.I., Russ. Chem. Rev., 1991, vol. 60,
5
6
no. 4, p. 391.
4. Kolodiazhnyi, O.I. Phosphorus Ylides. Chemistry and
Application in Organic Synthesis. Weinheim; New
York; Chichester: J. Wiley-VCH, 1999. 565 p.
5. Kolodiazhnyi, O.I., Tetrahedron Lett., 1985, vol. 26,
no. 4, p. 439. DOI: 10.1016/S0040-4039(00)61905-6.
6. Kolodiazhnyi, O.I., Tetrahedron Lett., 1981, vol. 22,
2
2
2
2
7
8
. Holstein, S.A., Cermak, D.M., Wiemer, D.F., Lewis, K.,
and Hohl, R., J. Bioorg. Med. Chem., 1998, vol. 6, no. 6,
p. 687. DOI: 10.1016/S0968-0896(98)00034-0.
no. 13, p. 1231. DOI: 10.1016/S0040-4039(01)90282-5.
7. Kolodiazhnyi, O.I., Zh. Obshch. Khim., 1986, vol. 56,
no. 2, p. 253.
9
. Lazrek, H.B., Witvrouw, M., Pannecouque, C., and De
Clerq, E., Tetrahedron, 1998, vol. 54, no. 15, p. 3807.
DOI: 10.1016/S0040-4020(98)00107-0.
8. Zhong, P., Xiong, Z.X., and Huani, X., Synth. Commun.,
2
0
000, vol. 30, no. 2, p. 273. DOI: 10.1080/
0397910008087318.
1
1
0. Harnden, M.R., Parkin, A., Parratt, M.J., and Perkins, R.M.,
2
3
9. Xu, Y., Flavin, M.T., and Xu, Z.-Q., J. Org. Chem.,
996, vol. 61, no. 21, p. 7697. DOI: 10.1021/jo9608275.
J. Med. Chem., 1993, vol. 36, no. 10, p. 1343. DOI:
1
1
0.1021/jm00062a006.
0. Blaszczyk, R., and Gajda, T., Heteroatom Chem., 2007,
1. Raboisson, P., Baurand, A., Cazenave, J.-P., Gachet, C.,
Schutz, D., Spiess, B., and Bourguigon, J.-J., J. Org.
Chem., 2002, vol. 67, no. 23, p. 8063. DOI: 10.1021/
jo026268l.
vol. 18, no. 7, p.732. DOI: 10.1002/hc.20371.
31. Brunner, H., Le Cousturier de Courcy, N., and Genêt, J.-P.,
Synlett, 2000, no. 2, p. 201. DOI: 10.1055/s-2000-6482.
1
2. Enders, D., Wahl, H., and Papadopoulos, K., Tetra-
hedron, 1997, vol. 53, no. 23, p. 12961. DOI: 10.1016/
32. Kolodiazhnyi, O.I., and Golokhov, D.V., Zh. Obshch.
Khim., 1987, vol. 57, no. 11, p. 2640.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 2 2015