Pyridinium perchlorate: A new catalyst for the reaction of trialkyl phosphites with the C=X electrophiles

Article abstract of DOI:10.1134/S107036321102006X

Pyridinium perchlorate is an effective catalyst for the reaction of trialkyl phosphites with various C=X electrophiles: aldehydes, ketones, ketophosphonates, imines, isocyanates, isothiocyanates, and activated alkenes. The reaction leads to the formation

Full text of DOI:10.1134/S107036321102006X

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 2, pp. 307–314. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © O.O. Kolodyazhnaya, O.I. Kolodyazhnyi, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 2, pp. 207–214.
Pyridinium Perchlorate: A New Catalyst for the Reaction
of Trialkyl Phosphites with the C=X Electrophiles
O. O. Kolodyazhnaya and O. I. Kolodyazhnyi
Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 1, Kiev, 02094 Ukraine
e-mail: olegkol321@rambler.ru
Received August 26, 2010
Abstract—Pyridinium perchlorate is an effective catalyst for the reaction of trialkyl phosphites with various
C=X electrophiles: aldehydes, ketones, ketophosphonates, imines, isocyanates, isothiocyanates, and activated
alkenes. The reaction leads to the formation of α-substituted phosphonates in a high yield. Advantages of the
new catalyst are its high activity, availability, high product yields, and mild reaction conditions.
DOI: 10.1134/S107036321102006X
The synthesis of functionalized phosphonates has
attracted much attention because of their high
biological activity [1–3]. They act as mimetics of
peptides, haptens of catalytic antibodies, antibiotics
and pharmaceuticals, herbicides and enzyme inhibitors
[4]. There are two main methods of synthesis of α-
functionalized phosphonates: the reaction of dialkyl
phosphites with unsaturated C=X electrophiles in the
presence of Brønsted bases or Lewis acids (Abramov
reaction [5, 6], Kabachnik–Fields reaction [7, 8], the
Pudovik reaction [9, 10] etc.), and the reaction of
trialkyl phosphites with aldehydes or imines in the
presence of Lewis acids [7, 11]. However, despite the
potential usefulness of these methods, they have several
disadvantages, such as, for example, low activity com-
pared to dialkyl phosphites toward ketones and ketimines.
The reactions are accompanied by the formation of
impurities appearing under the influence of alkaline
catalysts (phosphate–phosphonate rearrangement [11],
retro-Abramov reaction [12], and others). In addition,
Lewis acids used as catalysts are sensitive to moisture
and require very careful handling.
In this article we offer pyridinium perchlorate as a
new effective catalyst for the phosphonylation of the
C=X electrophiles (X = O, C, N, CR2) with trialkyl
phosphites. This probably is the first time that
ammonium or pyridinium salts are used as catalysts of
the reaction of trialkyl phosphites with electrophiles
[13, 14].
We recently reported that pyridinium halides
([C5H5NH]+Hlg–, where Hlg = Cl, Br, I) activate the
reaction of trialkyl phosphites with C=X electrophiles
[15]. The pyridinium perchlorate reminds pyridinium
halides by its action. The difference lies in the fact that
pyridinium halides act as reagents and are consumed in
the reaction with the formation of pyridine and alkyl
halide, while pyridinium perchlorate is a catalyst rather
than a reagent. It initiates the reaction of trialkyl
phosphite with C=X electrophile, but it is not
consumed in the reaction: The pyridinium perchlorate
can be isolated from the reaction mixture in the same
amount as introduced, and can be reused. No reduction
of the catalyst activity was observed.
R
R
EtO
EtO
EtO
EtO
[C5H5NH]+Hlg_
_C5H5N, _EtHlg
[C5H5NH]+ClO4_
_CH=CH2
R
R'
XH
R'
XH
P
(EtO)3P + X
P
R'
O
O
The scheme below underlain by the general
theoretical concepts on the mechanism of the reaction
of trialkyl phosphites with C=X electrophiles [1, 8],
suggests the following reasons of the catalytic effect of
pyridinium perchlorate. The nucleophilic attack of
triethyl phosphite on the electron-deficient carbon
307

308
KOLODYAZHNAYA, KOLODYAZHNYI
atom of the C=X group leads to the formation of
betaine A, which reacts with the pyridinium
perchlorate and is transformed into alkoxyphospho-
nium perchlorate B and pyridine. The salt B is unstable
and decomposes with the formation of phosphonate C,
alkene, and perchloric acid, which reacts with the
pyridine formed in the previous stage, regenerating the
catalyst. In contrast, the quasiphosphonium inter-
mediate D formed from pyridinium halide decomposes
liberating the alkyl halide.
R
EtO
ClO4_
+
P
EtO
R'
EtO
XH
[C5H5NH]+ClO4_
B
_CH=CH2
_HClO4
_C5H5N
R
EtO
EtO
R
R
X_
R'
+
(EtO)3P
R'
XH
(EtO)3P + X
P
_
R'
[C5H5NH]+Hlg
O
_EtHlg
A
C
_C5H5N
R
EtO
Hlg_
+
P
EtO
EtO
R'
XH
D
The pyridinium perchlorate initiates the reaction
with alkyl electrophiles C=X more actively than
pyridinium halides. The use of pyridinium perchlorate
instead of halides increases the reaction rate and the
yield of the reaction products. In all cases with
pyridinium perchlorate as a catalyst the reaction pro-
ceeded smoothly without solvent or in a methylene
chloride solution at room temperature with the
formation of α-substituted phosphonates without un-
wanted impurities (see the table) [14].
The pyridinium perchlorate can be easily prepared
by the reaction of pyridine with perchloric acid in
aqueous solution. The salt is poorly soluble in water
and precipitated in a high yield as a crystalline
substance. After filtering and drying in a vacuum
desiccator, the pyridinium perchlorate is ready for use.
Below are presented typical examples of the synthesis,
demonstrating the high efficiency of pyridinium
perchlorate as a catalyst for the reaction of trialkyl
phosphites with the C=X electrophiles. This very
active catalyst allows phosphonylation of some low-
active electrophiles, which are difficult to turn into
phosphonates by the other methods. The results are
presented in the table.
[C5H5NH] +X–
X = Cl X = Br
X = I
6
X = ClO4
Reaction duration, h
Temperature, °C
Yield of XI, %
12
35
55
12
35
70
5
25
92
25
85
R2
R3
R2
H
R2CH=O
(R1O)2P(O)
R2R3C=O
(R1O)2P(O)
OH
OH
VIII_XII
I_VII
(R1O)3P
R2
R1
NR2
+
O
R2
R2
R1
NHR1
(R1O)2P(O)
R2
ClO4_
(R1O)2P(O)
[(R1O)2P(O)]2C
OH
+
N
H
CH2=CHCH2N=C=S
PrN=C=O
XV, XVI
ХIII, ХIV
H
N
H
PhCH=CHNO2
(EtO)2P(O)
(EtO)2P(O)
N
(R1O)2P(O)CH(Ph)CH2NO2
S
O
XVIII
XVII
ХIХ
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

PYRIDINIUM PERCHLORATE: A NEW CATALYST
309
Products yield and the conditions of reaction (R1O)3P + R2R3C=X + [C5H5NH]+ ClO4– → (R1O)2P(O)C(XH)R2R3
Comp. no.
R1
R2
R3
H
X
O
Т, °C
Duration, h Yield, %
O
O
Me
0–20
2
89
I
Et
H
H
O
O
0–20
0–20
2
2
88
85
II
t-BuOC(O)NH
Me
III
N
COOBu-t
Et
Et
H
H
O
O
0–20
0–20
4
4
90
90
IV
V
Et
Et
H
H
O
O
0–20
0–20
2
2
90
90
VI
VII
Et
Et
3-F3CC6H4
Me
Me
O
O
25
25
6
80
70
VIII
IX
4-t-BuC6H4
12
Et
Et
Et
3,4-(MeO)2C6H3
–(СН2)5–
Et
O
O
O
50
4
12
85
85
80
X
25
25
XI
XII
–СH2CH2OCMe2CH2–
4
Et
(EtO)2P(O)
O
25
25
10
70
75
XIII
Et
(EtO)2P(O)
O
6
XIV
N
COOMe
Et
Н
PhN
30
12
60
XV
Me
Et
Ph
Ph
H
H
BnN
CHNO2
O
28
12
6
71
65
90
80
XVI
0–20
0–20
0–20
XVII
XVIII
XIX
Et
PrN=C
2
Et
CH2=CHCH2N=C
S
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

310
KOLODYAZHNAYA, KOLODYAZHNYI
Several aldehydes, including aromatic, aliphatic,
perchlorate in most cases proceeds under mild condi-
tions leading to the formation of the hydroxyphos-
phonates VIII–XII in a good yield.
and unsaturated aldehydes, readily react with trialkyl
phosphites in the presence of pyridinium perchlorate
with the formation of α-hydroxyphosphonates I–VII in
high yields. The reaction is exothermic and therefore it
is carried out at cooling below 0°C. No formation of
unwanted by-products was observed. Only a small
admixture of dialkyl phosphite was formed in case of
the penetration of moisture from the environment into
the reaction mixture, but the dialkyl phospite admixture
can be easily removed by heating (70–100°C) in a
vacuum that allows the preparation of spectro-
scopically pure hydroxyphosphonates I–VII even
without additional treatment.
In the presence of pyridinium perchlorate, keto-
phosphonates react with trialkylalkyl phosphites in
methylene chloride at room temperature or at cooling
to 0°C, to form 1-hydroxy-1,1-bisphosphonates (XIII,
XIV) [15, 16]. The reaction completes in a few hours
giving hydroxy-bisphosphonates XIII and XIV in a
high yield. These compounds being the derivatives of
terpenes and amino acids are of interest as potential
biologically active substances. Chiral bisphosphonate
(S)-XIV was obtained from the N-Moc-L-proline acid
chloride XX [17]. N-Moc-L-prolinoyl chloride XX
reacts readily with triethyl phosphite to form the chiral
ketophosphonate (S)-XXI, which was purified by
vacuum distillation and then transformed in a good
yield into the bisphosphonate (S)-XIV by the reaction
with triethylphosphite in the presence of pyridinium
perchlorate.
The pyridinium perchlorate initiates the reaction of
triethyl phosphite with ketones. This reaction usually
gives low yields of hydroxyphosphonate at the use of
dialkiphosphites because of their low reactivity. Due to
the high activity of the catalyst, the reaction of trialkyl
phosphites with ketones in the presence of pyridinium
H
H
H
_
(EtO)3P/[PyH]+ClO4
(EtO)3P
91%
P(O)(OEt)2
P(O)(OEt)2
Cl
P(O)(OEt)2
82%
N
N
N
O
O
OH
Moc
(S)-(_)-XX
Moc
Moc
(S)-(_)-XXI
(S)-(_)-XIV
Moc-MeOCO
The reaction of (EtO)3P/[PyH]+ClO4– with imines
leads to the formation of aminophosphonates (XV,
XVI) under mild conditions (see the table) [18]. The
reaction proceeds at 0°C, that is, easier than the
Kabachnik–Fields reaction described in literature
between the benzylbenzaldimine and diethyl phosphite
requiring the heating at 140°C over several hours.
Triethyl phosphite in the presence of pyridinium
perchlorate phosphonylates also ketimines that is
difficult to reach by other methods (see the table) [19].
Thus pyridinium perchlorate is a new effective
catalyst for the reaction of trialkyl phosphites with the
C=X electrophiles. The use of pyridinium perchlorate
allows the phosphonylation of aldehydes, ketones,
aldimines and ketimines, ketophosphonates, and some
of alkenes with the formation of functionalized
phosphonates. Pyridinium perchlorate is stable,
convenient in handling, can be easily separated by
filtration and is suitable for reuse as a catalyst. The
advantages of the developed procedure is the
preparative simplicity, a wide range of substrates used
and high yields of products. In many cases, pyridinium
perchlorate allows the preparation of functionalized
phosphonates, which are difficult or even impossible to
obtain by known methods.
Pyridinium perchlorate initiates the reaction of
nitrostyrene with trialkyl phospites in a methylene
chloride solution at 0°C with the formation of β-nitro-
α-phenylethylphosphonate XVII in a good yield [20]
Triethyl phosphite in the presence of [PyH]+ClO4–
phosphonylates isocyanates and isothiocyanates at 0°C
in a methylene chloride solution, turning them into
carbamoylphosphonates XVIII or thiocarbamoylphos-
phonates XIX in high yields.
EXPERIMENTAL
Melting points are uncorrected. The NMR spectra
were recorded on a Varian VXR-300 spectrometer at
300 (1H) and 126.16 (31P) MHz with internal TMS
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

PYRIDINIUM PERCHLORATE: A NEW CATALYST
311
(1H) and 85% H3PO4 in D2O (31P) as references. All
chemical shifts are expressed in δ scale (ppm). The IR
spectra were taken from KBr pellets or solutions in
CCl4 on a Vertex 70 IR Fourier spectrophotometer.
stirred for the time and at the temperature specified in
the table. The mixture was then filtered, diluted with
diethyl ether, and filtered again to separate ~0.0049 mol
of pyridinium perchlorate. The solvent was evaporated
and the residue was purified either by distillation in a
vacuum, or crystallized, or subjected to chromato-
graphy on a silica gel column.
Thin layer chromatography was performed on
aluminum plates with silica gel (0.25-mm layer) with
the spots detection under UV irradiation. The column
chromatography was carried out on Merck 60 silica
gel. In reactions anhydrous solvents were used: THF
was freshly distilled over sodium in the presence of
benzophenone, methylene chloride was distilled over
P4O10. Reagents were purchased from Merck and used
without special purification.
Reuse of the catalyst. The pyridinium perchlorate
used in the previous experiment and isolated was
washed with diethyl ether and dried in a vacuum. Then
the regenerated pyridinium perchlorate (~0.005 mol)
was added to the mixture of triethyl phosphite
(0.01 mol) and piperonal (0.01 mol) at cooling to 0°C,
and the reaction mixture was stirred for 2 h at room
temperature. The catalyst was separated (~0.0049–
0.005 mol), the residue was distilled in a vacuum. The
resulting diethyl (1,3-benzodioxol-5-yl)-hydroxy-
methylphosphonate was isolated in 85% yield, bp 160°C
(0.05 mm Hg), mp 83°C. Colorless crystalline
substance. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.14–1.27 m, (6H, CH3), 3.94–4.08 m (4H, OCH2),
5.00 d (J = 11.0, 1H, PCH), 7.25–7.4 m (3H, C6H3).
31P NMR spectrum (CDCl3), δ, ppm: 21.69. Found, %:
P 10.59. C12H17O6P. Calculated, %: P 10.75.
Pyridinium perchlorate. To 0.1 mol of pyridine in
100 ml of water at stirring and cooling to 0°C was
added 0.1 mol of 10% perchloric acid solution in
water. The mixture was stirred for 15–20 min at this
temperature, then the formed white crystalline product
was filtered off or the reaction mixture was kept in a
refrigerator for 2 h for complete separation of
pyridinium perchlorate from the reaction mixture and
the formation of the best crystals, then filtered, and the
solid was washed on the filter with a small amount of
water cooled to 0°C. The product was dried first in a
vacuum of 0.05 mm Hg, and then overnight in a
vacuum desiccator over phosphorus pentoxide. Yield
85–90%, mp > 250 °C. 1H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 7.5–8.5 m (C6H5N). Found, %: Cl 19.4.
C5H6ClNO4. Calculated, %: Cl 19.77
Similarly, the reaction of triethyl phosphite with
cyclohexanone catalyzed by the regenerated pyridi-
nium perchlorate gave diethyl 1-hydroxycyclohexyl-
phosphonate (XI). 85% yield, bp 120°C (0.08 mm
Hg), mp 61–63°C. 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 1.3 m (6H, J = 7.2, CH3), 1.52 m (2H, CH2),
1.66 m (4H, CH2), 1.87 m (4H, CH2), 3.6 m ( 1H, OH),
4.16 d.q (4H, J = 7, J = 8, OCH2). 13C NMR spectrum
(CDCl3), δ, ppm (J, Hz): 16.45 d (J = 6.25), 20.20 d
(J = 11.5), 25.37, 31.51 d (J = 2.5, CH2), 62.51 q (J =
Addition of trialkyl phosphites to aldehydes in
the absence of solvent (general procrdure). The
pyridinium perchlorate (~0.005 mol) was added to a
mixture of aldehyde (0.01 mol) and trialkyl phosphite
(0.01 mol) at cooling to 0°C, the reaction mixture was
stirred for the time specified in the table. Then the
reaction mixture was extracted with methylene
chloride or diethyl ether and filtered. As a result,
~0.0049 moles of the used catalyst was separated. The
solvent was evaporated in a vacuum of 10 mm Hg and
then if necessary the residue was maintained in a
vacuum of 0.05 mm Hg at 70–100°C, the product
obtained was used without additional treatment or
either distilled in a vacuum, or crystallized, or sub-
jected to chromatography on a silica gel column.
31
7.5, OCH2), 70.95 q (J = 147.5, PC). P NMR spec-
trum (CDCl3), δ, ppm: 26.9 [15].
Dimethyl (1,3-benzodioxol-5-yl)hydroxymethyl-
phosphonate (I). Colorless crystalline substance, mp
91°C (CHCl3 / hexane). 1H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 3.7 d (J = 15, CH3O), 5.36 d (J = 10,
HCH), 5.91 s (3H, CH2O2), 7.2–7.4 m (5H, C6H3). 13C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 53.0 d (J =
28), 70.1 d (165), 101.1, 107.9 d (J = 21), 120, 130,
147.48, 147.68. 31P NMR spectrum (CDCl3), δ, ppm:
28.1. Found, %: C 46.34, H 5.21. C10H13O6P.
Calculated, %: C 46.16, H 5.04.
Addition of trialkyl phosphites to aldehydes in a
solvent (general procrdure). The pyridinium
perchlorate (~0.005 mol) was added to a solution of
C=X compounds (0.01 mol) and trialkyl phosphite
(0.01 mol) at cooling to 0°C, the reaction mixture was
Diethyl N-tert-butoxycarbonyl-3-amino-1-hyd-
roxypropilphosphonate (II). Colorless oil, bp 160°C
1
(0.008 mm Hg). H NMR spectrum (CDCl3), δ, ppm
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011

312
KOLODYAZHNAYA, KOLODYAZHNYI
(J, Hz): 1.34 t (6H, J = 7 CH3), with 1.44 [9H, (CH3)3C],
1.89 m (2H, CH2), 3.23 m (1H, NCH2), 3.46 m (1H,
NCH2), 3.96 m (1H, PCH), 4.18 m (OCH2), 5.1 br (1H,
CH2), 1.6 m (4H, CH2), 1.8 m (2H, CH2), 1.9 m (1H,
CH), 2.0 m (1H, CH) , 2.19 m (2H, CH2) 2.91 br (1H,
OH), 4.2 m (5H, CH2O + PCH). 13C NMR spectrum
(CDCl3), δ, ppm (J, Hz): 16.4, 19.27, 19.99, 24.87,
27.02, 27.07, 28.01, 28.97, 32.89, 33.73, 39.5, 48.9,
62.17 d (J = 6), 62.17, 70.88 d (J = 160), 127.2,
133.61. 31P NMR spectrum (CDCl3), δ, ppm: 25.63 [15].
13
OH). C NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.
4, 28.5, 33.0, 35.0, 62.05 d (J = 8), 64 d (J = 160). 31P
NMR spectrum (CDCl3), δ, ppm: 25.7. Found, %: N
4.55, P 9.81. C12H26NO6P. Calculated, %: N 4.50, P
9.95.
Diethyl
(2E)-1-hydroxy-3,7-dimethyl-2,6-octa-
Diethyl (S,R)-2-N-Boc-pyrrolidinehydroxymethyl-
phosphonate (III). To 0.01 mol of trimethyl phosphite
at –10°C was added 10 mmol of N-Boc-prolinal and 6
mmol of pyridinium perchlorate. The reaction mixture
was stirred for 5 h at –10°C, 2 h at 0°C, and 1 h at
room temperature, then diluted with diethyl ether and
filtered, the residue was evaporated. The product yield
95%, a mixture of (S,R)- and (S,S)-diastereoisomers in
the ratio 4:1. 31P NMR spectrum (CDCl3), δ, ppm: 26.9
and 26.3. The product was purified by chromatography
on silica gel column (EtOAc–hexane, 1:3) and then
repeatedly recrystallized from the mixture of hexane
and chloroform with cooling to –20°C, and then from
hexane. (S,R)-diastereomer III was obtained, mp 79°C,
[α]D –60° (c 2, CHCl3). 1H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 1.42 s [9H, (CH3)3C], 1.8–2.3 m (4H,
CH2) 3.2 m (1H, PCH), 3.7–3.8 m (2H, CH2N ), 3.7 d
(6H, J = 10, CH3O), 4.1 m (1H, NCH). 13C NMR
spectrum (CDCl3), δ, ppm (J, Hz): 24.5, 28.5, 28.8,
47.5, 53.0 d (J = 6.9), 59.0, 73.5 d (J = 158.8), 81.5,
159. 31P NMR spectrum (CDCl3), δ, ppm: 26.9
[15,16].
dienylphosphonate (VI). Yield 80%, bp 135°C
(0.08 mm Hg). H NMR spectrum (CDCl3), δ, ppm (J,
1
Hz): 1.28 m (3H, JHH = 7, CH3), 1.29 m (3H, JHH = 7,
CH3), 1.61 s (3H, CH3), 1.69 s (3H, CH3), 2.1 br (4H,
CH2), 4.12 m (4H, OCH2) 4.52 d.d (1H, JHH = 9,
J
HP = 9) 5.12 br (1H, CH=C), 5.36 br (1H, CH=C). 13C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.4, 17.0,
17.6, 25.60, 07.26, 37.90, 37.9, 61.7, 61.8, 65.1, 66.1,
119.1, 124.0, 131.7, 138.8. 31P NMR spectrum
(CDCl3), δ, ppm: 24.19 [15].
Diethyl (SP/R, R/RP)-(6E)-1-hydroxy-3,7-dimethyl-
2,6-octenylphosphonate (VII). Yield 80%, bp 145–
150 on C (0.08 mm Hg.). A mixture of (SP/R, R/RP)-
1
diastereoisomers. H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 0.96 d, (3H, J = 7, CH3), 1.29 m (3H, J = 7,
CH3), 1.30 m (3H, J = 7, CH3), 1.58 s (3H, CH3) 1.65 s
(3H, CH3), 1.83 m (2H, CH2), 1.96 m (2H, CH2), 3.82
m (1H, CH), 4.09 m (4H, OCH2), 5.07 m (1H, J = 7,
CH=C), 5.7 br (1H, OH). 13C NMR spectrum (CDCl3),
δ, ppm (J, Hz): (SP/R), 16.45, 16.49, 17.06, 20.25,
25.19, 25.52, 25.65, 28.30 d (J = 12), 35.75, 38.11,
62.51 d (J = 7.5), 62.64 d (J = 6), 65.59 d (J = 158),
124.70, 131.09. (RP/R), 16.45, 16.49, 18.35, 20.25,
25.19, 25.52, 25.65, 29.0 d (J = 12), 37.80, 38.56,
62.51 d (J = 7.5), 62.64 d (J = 6), 66.06 d (J = 157),
124.72, 131.13. 31P NMR spectrum (CDCl3), δ, ppm:
26.50, 26.54. Found, %: P 10.69. C14H29O4P.
Calculated, %: P 10.59.
Diethyl hydroxy[6-methyl-4-(4-methylpentene-3-
enyl)cyclohexyl-3-en-1-yl]methylphosphonate (IV).
Yield 80%. The product was purified by chromato-
graphy on a silica gel column (EtOAc–hexane, 1:3).
1
Colorless oil, bp 180°C (0.08 mm Hg). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 0.99 d (3H, J = 6,
CH3), 1.33 m (6H, J = 7, CH3 CH2), 1.6 s (3H, CH3),
1.87 s (3H, CH3), 1.91–2.22 m (10H, CH2 + CH), 3.51
br (OH), 4.17 m (5H, J = 7, J = 8, OCH2 + PCH), 6.28
s (1H, CH=C), 5.32 m (2H , CH=C). 13C NMR
spectrum (CDCl3), δ, ppm (J, Hz): 8.87, 16.28, 17.3,
25.4, 25.78, 27.01, 27.08, 29.96, 32.15, 33.69 d (J =
150), 42.8, 61.81 d (J = 6), 120.6, 123.9, 130.8,
135.59. 31P NMR spectrum (CDCl3), δ, ppm: 26.6 [15].
Diethyl 1-hydroxy-1-(3-trifluoromethylphenyl)-
ethylphosphonate (VIII). Yield 80%. The product
was purified by crystallization from hexane. Colorless
1
crystals, mp 125–128°C. H NMR spectrum (CDCl3),
δ, ppm (J, Hz): 1.24 m (6H, J = 7, CH3), 1.83 d (3H,
J = 15.6, CH3CP), 4.04 m (2H, OCH2), 4.12 m (2H,
13
OCH2), 4.66 br (1H, NH), 7.44–7.9 m (4H, C6H4). C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.17, 26.33,
63.5 d (J = 94), 73.5 d (J = 161), 127 q (J = 271),
123.1, 123.88, 128.16, 130.01, 130.27, 143.00. 19F
NMR spectrum (CDCl3), δ, ppm: –57.67. 31P NMR
spectrum (CDCl3), δ, ppm: 25.3 d (J = 8). Found, %: C
47.55, H 5.50, P 9.65. C13H18F3O4P. Calculated, %: C
47.86, H 5.56, P 9.49.
Diethyl hydroxy(3,8,8-trimethyl-1,2,3,4,5,6,7,8-
octahydronaphth-2-yl)methylphosphonate (V). Yield
80%. Colorless crystals, bp190°C (0.1 mm Hg), mp
1
107–110°C (hexane). H NMR spectrum (500 MHz,
CDCl3): 0,957 d (3H, J = 6, CH3 C), 0.975 s (6H, m-
CH3), 1.34 m (6H, J = 7, CH3CH2O), 1.43 m (2H,
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PYRIDINIUM PERCHLORATE: A NEW CATALYST
313
Diethyl 1-hydroxy-1-(4-tert-butylphenyl)ethyl-
phosphonate (IX). Yield 80%. Colorless crystals, mp
84–86°C (hexane). 1H NMR spectrum (CDCl3), δ, ppm
(J, Hz): 1.15 m (3H, CH3) 1.17 m (3H, CH3), 1.24 s
[9H, (CH3)3C)], 1.8 d (J = 14.5, CH3), 3.93 m (2H,
OCH2), 4.07 m (2H, OCH2), 7.3–7.5 m (4H, C6H4). 13C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.35, 25.83,
31.34, 34.44, 63.26 d (J = 16), 73.4 d (J = 158), 124.9,
125.55 d (J = 4), 137.88, 150.24. 31P NMR spectrum
(CDCl3), δ, ppm: 26.0. Found, %: C 61.01, H 8.75, P
9.65. C16H27O4P. Calculated, %: C 61.13, H 8.66, P
9.85.
purified by chromatography on silica gel column
(EtOAc–hexane, 50:50). Yield 65%, oil. H NMR
1
spectrum (CDCl3), δ, ppm (J, Hz): 1.27 t (6H, J = 7,
CH3) 1.28 t (6H, J = 7, CH3), 1.6 s (3H, CH3), 1.63 s
(3H, CH3), 1.8 d (3H, JHH = 8, CH3), 2.0 m (4H, CH2),
4.21 m (8H, OCH2), 4.8 m (1H, CH=), 5.1 m (1H,
JHH = 7, CH=). 13C NMR spectrum (CDCl3), δ, ppm:
16.21, 16.41, 17.59, 17.81, 25.61, 26.87, 36.9, 60.93,
64.53, 67.83, 71.13, 115.5, 124.03, 131.67, 139.77. 31P
NMR spectrum (CDCl3), δ, ppm: 23.3. Found, %: C
50.45, H 8.41, P 14.40. C18H36O7P2. Calculated, %: C
50.70, H 8.51, P 14.53.
Diethyl
[1-(3,4-dimethoxyphenyl)-1-hydroxy-
Bis(dietoxyphosphinyl)hydroxymethyl-N-(meth-
oxycarbonyl)-1-pyrrolidine (XIV). Rf 0.15 (EtAc :
propyl]phosphonate (X). The product was purified by
column chromatography on silica gel (EtOAc–hexane
1:3). Colorless oil, Rf 0.33, yield 60%. H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 0.77 t (3H, J = 7.2,
CH3), 1.15 t (3H, J = 7, CH3CH2O), 1.27 t (3H, J = 7,
CH3CH2O), 2.13 d.q (1H, PCCH, J = 7, J = 8), 2.24
d.q (1H, PCCH, J = 7, J = 8), 3.87 s, 3.89 s (3H,
20
1
MeOH : C6H12 = 1:1:1). [α]D –59° (c 3.5, CHCl3). H
NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.37 m (12H,
CH3), 1.68 m, 1.91 m (2H, CH2), 2.37 m, 2.65 m (2H,
CH2), 3.39 m (2H, CH2N), 3.75 s (3H, CH3O), 4.3 m
(8H, OCH2), 4.4 m (1H, CHN). 13C NMR spectrum
(CDCl3), δ, ppm (J, Hz): 16.3, 23.63, 29.50, 47.69,
53.18, 63.07, 63.23 s, 63.29, 63.50, 64.05 t, J = 62
(CHN), 79.3 t (J = 153), 159.4. 31P NMR spectrum
(CDCl3), δ, ppm: 21.72, 21.57, 20.94, 20.80 (rotamers
and magnetic nonequivalence). MS APCI, m/z: 432.3
(M + 1). Calculated: M 431.3.
1
13
CH3O), 4.1 m (4H, CH2O), 6.9–7.5 m (3H, C6H3). C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 9.09, 16.45,
27.82, 55.97, 62.35, 71.93, 72.94, 114.35, 116.59,
123.85, 125.3, 150.31, 151.02. 31P NMR spectrum
(CDCl3), δ, ppm: 24.3. Found, % 54.16, H 7.54.
C15H25O6P. Calculated, %: C 54.21, H 7.58.
Diethyl 1-(benzylamine)benzylphosphonate (XV).
Diethyl 1-hydroxycyclohexylphosphonate (XI).
1
Yield 70%, bp 150°C (0.02 mm Hg). H NMR
Yield 80%, bp 120°C (0.1 mm Hg), mp 71–73°C
1
spectrum (CDCl3), δ, ppm (J, Hz): 1.20 d (3H, J = 7,
CH3), 1.30 d (3H, J = 7, CH3), 5.2 d (1H, J = 24,
PCH), 6.8–7.28 m (5H), 7.3 d (2H, J = 8.5), 7.5 d (J =
8.5, 2H). 31P NMR spectrum (CDCl3), δ, ppm: 24 [18].
(hexane). H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.3 t (6H, J = 7.2, CH3 CH2), 1.52 m (2H, CH2) 1.66 m
(4H, CH2), 1.87 m (4H, CH2), 3.6 br (1H, OH), 4.16
d.q (4H, J = 7, J = 8, OCH2). 13C NMR spectrum
(CDCl3), δ, ppm (J, Hz): 16.45 d (J = 6.25), 20.22 d
(J = 11.5), 25.37, 31.5 d (J = 2.5), 62.5 d (J = 7.5) ,
70.95 d (J = 147.5). 31P NMR spectrum (CDCl3), δ,
ppm: 26.93 [15].
Diethyl (2E)-1-anilino-3,7-dimethylocta-2,6-dienyl-
phosphonate (XVI). The product was purified by
chromatography on a silica gel column. Oil. Yield
1
50%. H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.27–1.17 m (6H, CH3), 1.49 s (3H, CH3), 1.54 s (3H,
CH3), 1.61 s (3H, CH3), 1.72–1.71 m (2H), 2.06–1.97
Diethyl hydroxy-4-(tetrahydro-2,2-dimethyl-2H-
pyran-4-yl)phosphonate (XII). Yield 80%, bp 130–
135°C (0.08 mm Hg), mp 72–75°C. 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 1.19 s [3H, (CH3)2C], 1.43 s
[3H, (CH3)2C], 1.64–19 m (4H, CH2), 3.65 m (2H,
CH2O), 3.95 br (1H, OH), 3.65 m (1H, CH2), 4.05 m
1
m (2H), 4.15–3.97 m (4H, CH2), 4.38 d.d (1H, JPH
3
20.7, JCH 9.4, PCH), 4.95–5.12m (2H, C=CH), 7.13–
6.54 m (5H, C6H5). 13C NMR spectrum (CDCl3), δ,
ppm (J, Hz): 16.4, 16.5, 17.1, 17.7, 25.6, 26.2, 39.6,
50.6 d (J = 158.5), 62.8 d (J = 7.3), 63.1 d (J = 6.6),
113.9, 118.4, 119.9, 123.6 , 129.1, 131.8, 141.6, 146.8.
31P NMR spectrum (CDCl3), δ, ppm: 28.4 [19].
13
(1H, CH2), 4.15 d.q (4H, J = 7, J = 8, CH3CH2O). C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.45, 24.29,
31,909, 32.61, 39.87, 56.1 d (J = 12.5), 62.8 d (J =
8.5), 63.0 d (J = 7.5), 70 d (J = 183.5), 70.57. 31P
NMR spectrum (CDCl3), δ, ppm: 23.6. Found, %: P
11.63. C11H23O5P. Calculated, %: P 11.63.
Diethyl (2-nitro-1-phenyl)ethylphosphonate (XVII).
Yield 70%, mp. 65°C (hexane). 13C NMR spectrum
(CDCl3), δ, ppm: 16.2, 37.46, 37.94, 61.74, 78.35,
31
127.3, 128, 128.9, 133.7. P NMR spectrum (CDCl3),
Tetraethyl (E)-1-hydroxy-3,7-dimethylocta-2,6-
diene-1,1-diyldiphosphonate (XIII). The product was
δ, ppm: 28.0 [20].
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314
Diethyl
KOLODYAZHNAYA, KOLODYAZHNYI
3. Kolodyazhnyi, O.I., Usp. Khim., 2006, vol. 75, no. 3,
(propylamino)carbonylphosphonate
p. 254.
(XVIII). Yield 90%, colorless oil, bp100–110°C
(0.08 mm Hg). H NMR spectrum (CDCl3), δ, ppm (J,
Hz): 0.87 t (3H, J = 7.5, CH3), 1.3 t (6H, J = 7,
CH3CH2O), 1.51 m (2H, CH3CH2CH2), 3.2 q (4H, J =
7, NCH2), 4.15 m (4H, CH2O): 7.34 m (1H, NH). C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 11.2 d (J =
8), 16.15 d (J = 15), 22.6, 40.98, 64.15 d (J = 8), 165 d
(J = 221). P NMR spectrum (CDCl3), δ, ppm: –0.71
1
4. Wiemer, D.F., Tetrahedron, 1997, vol. 53, no. 49,
p. 16609.
5. Abramov, V.S., Dokl. Akad. Nauk SSSR, 1954, vol. 95,
13
no. 5, p. 991.
6. Savignac, Ph. and Iorga, B., Modern Phosphonate
Chemistry, Boca Raton: CRS Press, 2003.
31
7. Galkina, I.V., Zvereva, E.R., Galkin, V.I., and
Cherkasov, R.A., Zh. Obshch. Khim., 1998, vol. 68,
no. 7, p. 1391.
[15.21].
Diethyl
(allylamino)tiocarbonylphosphonate
8. Cherkasov, R.A. and Galkin, V.I., Usp. Khim., 1998,
(XIX). Yellowish liquid. Yield 80%, bp 120°C
(0.08 mm Hg). H NMR spectrum (CDCl3), δ, ppm (J,
vol. 67, no. 10, p. 940.
9. Pudovik, A.N., and Konovalova, I.V., Synthesis, 1979,
1
Hz): 1.36 t (6H, CH3CH2), 4.08–4.3 m (6H, OCH2 +
NCH2), 5.27 d.d (1H, J = 6, J = 1, C=CH2), 5.31 d.d
(1H, J = 12.5, J = 1, C=CH2), d.d.t 5.91 (1H, J = 17,
J = 10.2, J = 6, CH2CH=C), 9.27 br (1H, NH). 13C
NMR spectrum (CDCl3), δ, ppm (J, Hz): 16.24 d (J =
10), 42.4 d (J = 9), 63 d (J = 6), 119, 130.7, 193 d (J =
155). 31P NMR spectrum (CDCl3), δ, ppm: –1.7 [15].
no. 2, p. 81.
10. Quin, L.D., A Guide to Organophosphorus Chemistry,
New York Wiley: Wiley, 2000, p. 146.
11. Hammerschmidt, F. and Schmidt, S., Monatsh. Chem.,
1997, vol. 128, p. 1173.
12. Gancarz, R., Gancarz, I., and Walkowiak, U., Phosph.,
Sulf., Silicon and Relat. Elem., 1995, vol. 104, no. 1,
p. 45.
13. Kolodyazhnaya, O.O., Kolodyazhnaya, A.O., and Kolo-
dyazhnyi, O.I., Abstract of Papers, Int. Conf. on
Phosphorus Chemistry (ICPC-2010), Wroclaw, 2010,
p. 156.
14. Kolodyazhnyi, O.I., Kolodyazhnaya, A.O., and Kolo-
dyazhnaya, O.O., Ukraine Patent no. 54008, 2010, Byul.
Izobrtet., 2010, no. 20.
15. Kolodyazhnaya, O.O., Kolodyazhnaya, A.O., and Kolo-
dyazhnyi, O.I., Zh. Obshch. Khim., 2010, vol. 80, no. 4,
p. 709.
16. Van der Veken, P. K., Senten, I., Kertèsz, A., and
Haemers, K.A., Tetrahedron Lett., 2003, vol. 44, no. 5,
p. 969.
17. Kolodyazhnaya, O.O. and Kolodyazhnyi, O.I., Zh.
Obshch. Khim., 2011, vol. 81, no. 1, p. 147.
18. Ambica, Kumar, S., Taneja, S.C., Hundal, M.S., and
Kapoor, K.K., Tetrahedron Lett., 2008, vol. 49, no. 14,
p. 2208.
Diethyl N-(methoxycarbonyl)-1-pyrrolidinoketo-
phosphonate (XXI). To 0.02 mol of N-Moc-L-proline
(XX) [17] was added 0.04 mol of triethyl phosphite at
–20°C. Then the temperature of the reaction mixture
was raised to 20°C, the mixture was stirred for 2 h and
then distilled in a vacuum. Yield 85%, bp 140°C
(0.08 mm Hg). Colorless liquid, [α]D20 –44 (c 2,
1
CHCl3). H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.37 m (6H), 1.9 m (2H), 2.2 m (2H), 2.2 (m, 2H),
3.59 s, 3.71 s (3H, CH2), 4.24 m (3H, OCH2), 4.81 m,
4.87 m (1H, CHN). 13C NMR spectrum (CDCl3), δ,
ppm (J, Hz): 17.8, 28.89, 29.31, 29.53, 30.63, 46.39,
46.90, 52.21, 52.27, 63.30, 63.35, 63.55, 63.61,
154.25, 155.04, 208.8 d (J = 157.5), 208.6 d (J = 160).
31P NMR spectrum (CDCl3), δ, ppm: –2.98 and –2.78
(rotamers). Found, %: N 4.61, P 10.67. C11H20NO6P.
Calculated, %: N 4.78, P 10.56.
19. Xia, M. and Lu, Y.-D., Ultrason. Sonochem., 2007,
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Izv. Akad. Nauk SSSR, 1972, no. 5, p. 1164.
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Obshch. Khim., 2010, vol. 80, no. 7, p. 1209.
2. Eymery, F., Iorga, B., and Savignac, P., Tetrahedron,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011