Facile Synthesis of 2-Aminocyclobutenylphosphonates

Article abstract of DOI:10.1134/S1070428020010212

The addition of various amines to diethyl 4-chlorobut-1-yn-1-ylphosphonate produced novel biologically potent substituted diethyl 2-aminocyclobut-1-en-1-ylphosphonates in 70–83% isolated yield. This regioselective reaction was carried out at room temperat

Full text of DOI:10.1134/S1070428020010212

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2020, Vol. 56, No. 1, pp. 137–142. © Pleiades Publishing, Ltd., 2020.
Facile Synthesis of 2-Aminocyclobutenylphosphonates
A. A. A. Al Quntara, b,*, H. Dweikb, and V. Dembitskyc
a Department of Material Engineering, Faculty of Engineering, Al-Quds University, Jerusalem, 90612 Palestine
b Faculty of Chemistry and Chemical Technology, Al-Quds University, Jerusalem, 90612 Palestine
c Centre for Applied Research, Innovation and Entrepreneurship, Lethbridge College,
South Lethbridge, Canada AB T1K 1L6
*e-mail: abedalaziz@staff.alquds.edu
Received August 21, 2019; revised November 17, 2019; accepted November 22, 2019
Abstract—The addition of various amines to diethyl 4-chlorobut-1-yn-1-ylphosphonate produced novel
biologically potent substituted diethyl 2-aminocyclobut-1-en-1-ylphosphonates in 70–83% isolated yield. This
regioselective reaction was carried out at room temperature in the absence of solvent and catalyst.
Keywords: vinylphosphonates, cyclobutenes, β-aminophosphonates, amine addition.
DOI: 10.1134/S1070428020010212
Cyclobutene derivatives are of particular interest as
organic units not only due to their intriguing molecular
skeleton suggesting specific properties such as a high
ring strain and consequent enhanced electrophilicity
but also because of their reactivities and importance as
intermediates in organic synthesis [1–3]. They undergo
electrocyclic ring-opening reaction to produce highly
electron-deficient 1,3-dienes [4], thermal aromatization
[5], and other transformations [6–18]. In addition, cy-
clobutene derivatives have wide utility as biologically
active compounds [19, 20]. For instance, they possess
anti-inflammatory [21–23], herbicidal [24], and anti-
tumor activity [25]. Moreover, they showed protective
properties against UV radiation [26], and other useful
properties [27].
alkynes [36], gold-catalyzed intermolecular reaction of
terminal alkynes with alkenes [37], cycloalkylation re-
actions involving (4-halo-1-alkenyl)metals [38], intra-
molecular Wittig reaction of vinyl(triphenyl)phospho-
nium salt with dioxobutanoates [4], thermolysis–
oxidation [39], and other reactions [40, 41].
Interestingly, the presence of a phosphonate group
on the cyclobutene ring enhances its biological activity
[42]. Despite that, not many methods have been yet re-
ported for the synthesis of cyclobutenylphosphonates.
Generally, they are produced from readily available
halogenated cyclobutenes via Arbuzov reaction
[43, 44] or by cyclizations of diazophosphonate
intermediates [45–48].
We previously synthesized cyclobutenylphospho-
nates by zirconation of 1-alkynylphosphonates, fol-
lowed by treatment with copper(I) chloride (Scheme 1)
[49]. In addition, cyclization reactions of ω-chloro-1-
alkynylphosphonates with amines were also found to
produce cyclic β-aminophosphonates as shown in
Scheme 2 [50].
During the last few decades several methods have
been developed for the preparation of polysubstituted
cyclobutenes. For example, they can be obtained by
photochemical [2+2]-cycloaddition of olefines and
acetylenes to cyclic enones and unsaturated lactones
[28–32], titanium-mediated intramolecular cyclization
of bis-propargyl alcohols [33], reaction of dilithiated
benzylacetylene with isothiocyanates [34], metallo-
cupration of allenes and acetylenes [35], zirconium-
mediated inter- or intramolecular cyclodimerization of
Being encouraged by these results, we focused on
the reaction of amines with an alkynylphosphonate
having a shorter alkynyl chain, in particular, with
Scheme 1.
R
R
P(O)(OEt)2
P(O)(OEt)2
2EtMgCl, Cp2ZrCl2, THF
2CuCl
78%
R
P(O)(OEt)2
ZrCp2
1
2
3
137

AL QUNTAR et al.
138
Scheme 2.
P(O)(OEt)2
P(O)(OEt)2
H
N
+
2
Cl
R1
R2
83–88%
( )n
NR1R2
( )n
4
5
R1, R2 = H, Alk, Ar; n = 1, 2.
Scheme 3.
n-BuLi, Et2
O
Cl
OH
Cl
SOCl2, reflux
–78°C to r.t.
HC
HC
Li
(EtO)2P(O)Cl
–78°C to r.t.
P(O)(OEt)2
Cl
6
Scheme 4.
NHPr
NHPr
H2/Pd, 28 psi
6
+
PrNH2
83%
P(O)(OEt)2
P(O)(OEt)2
8a
7a
diethyl (4-chlorobut-1-yn-1-yl)phosphonate (6) which butenylphosphonates were obtained by the addition of
was successfully prepared by substituting the hydroxy various amines to diethyl 4-chlorobut-1-yn-1-ylphos-
group in but-3-yn-1-ol using thionyl chloride under phonate (6). When the latter was allowed to react with
reflux. The product was isolated by distillation, dis- propylamine at 25°C for 15 h, diethyl [2-(propyl-
solved in diethyl ether, lithiated with n-BuLi, and amino)cyclobut-1-en-1-yl]phosphonate (7a) was
reacted with diethyl chlorophosphate (Scheme 3).
formed as the only product in 83% yield (Scheme 4).
Likewise, other primary and secondary amines were
reacted with phosphonate 6 under similar conditions to
obtain 2-aminocyclobutenylphosphonates 7b–7i which
were isolated by silica gel column chromatography in
good yields (70–83%; Table 1) and were characterized
by NMR, GC/MS, and elemental analyses. The
1H NMR spectra of 7a–7i showed two broad triplets in
the region δ 2.18–2.93 ppm along with vinylic carbon
signals at δC 68.9–217.2 ppm in the 13C NMR spectra.
The phosphorus atom of 7 resonated in 31P NMR
spectra at δP ~30 ppm.
We have developed an effective and facile method
for the synthesis of novel cyclobutenes. 2-Aminocyclo-
Table 1. Synthesis of diethyl 2-aminocyclobutenylphospho-
nates 7a–7i
NR1R2
P(O)(OEt)2
7a–7i
Compound no.
Amine
Yield,a %
7a
7b
7c
7d
7e
7f
Propylamine
83
81
80
75
73
80
78
77
70
Isopropylamine
tert-Butylamine
Benzylamine
This process represents a general and facile one-pot
method for the synthesis of novel oily 2-aminocyclo-
butenylphosphonates 7. Compounds 7a–7i are stable
on exposure to air at room temperature and are soluble
in most organic solvents. Apart from primary and
secondary amines, the described cyclization is also
tolerant to alkyl (7a–7c, 7f, 7i), aryl (7d, 7e, 7g), and
hydroxy groups (7h) as shown in Table 1.
Aniline
Methylamineb
2-Phenylethylamine
2-Aminoethanol
Diisopropylamine
7g
7h
7i
a
Isolated yield (after silica gel chromatography); in all cases,
the conversion was higher than 98% according to the GC/MS and
31P NMR data.
Compound 7a was smoothly hydrogenated over
Pd/C as a catalyst to afford cyclobutane derivative 8a
in a high yield. On the basis of our observations and
b
Methylamine was used as a 40% aqueous solution.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020

FACILE SYNTHESIS OF 2-AMINOCYCLOBUTENYLPHOSPHONATES
139
Scheme 5.
OEt
OEt
OEt
P
OEt
Cl
P
P
Cl
OEt
OEt
OEt
+
H+
P
OEt
O
O
O
NH2
O
NH2
NH
Me
Me
Me
NH2
Me
6
7f
previous theoretical calculations, we presumed that the
reaction proceeds by a stepwise mechanism where the
first step involves initial addition of the amine to the
triple bond to give zwitterionic intermediate, and the
next steps involve cyclization followed by elimination
of proton, leading to 2-aminocyclobut-1-en-1-ylphos-
phonates 7 [50] (Scheme 5).
phosphonate (0.22 g, 1 mmol) was mixed with iso-
propylamine (0.07 g, 1.1 mmol) in a 10-mL round-
bottom flask, and the mixture was stirred at 25°C for
15 h. The mixture was then washed with 0.1 N aqueous
sodium hydroxide and extracted with methylene
chloride (2×20 mL), the extract was dried over MgSO4
and concentrated on a rotary evaporator, and the
residue was purified by silica gel column chromatog-
In summary, novel biologically potent diethyl
2-aminocyclobut-1-en-1-ylphosphonates 7a–7i were
smoothly prepared by addition of amines to diethyl
4-chlorobut-1-yn-1-ylphosphonate. The reaction is
facile, general, and selective, it requires neither solvent
nor catalyst, and the products are formed in high yield.
This makes the described reaction a convenient method
for the synthesis of 2-aminocyclobutenylphosphonates
with the phosphorus and nitrogen substituents linked
to the neighboring double-bonded carbon atoms
(β-aminophosphonates).
1
raphy (CH2Cl2–MeOH, 9 : 1). H NMR spectrum, δ,
ppm: 1.12 d [6H, JHH = 6.3 Hz, CH(CH3)2], 1.26 t (6H,
JHH = 6.9 Hz, OCH2CH3), 2.63 br.t (2H, JHH = 6.9 Hz,
CH2CH2), 2.86 br.t (2H, JHH = 7.2 Hz, CH2CH2),
2.92 m [1H, CH(CH3)2], 4.11 m (4H, OCH2CH3).
31P NMR spectrum: δP 30.38 ppm. 13C NMR spectrum,
δC, ppm: 16.2 d (3JPC = 6.2 Hz, OCH2CH3), 21.4 s
[(CH3)2C)] 23.7 s (CH2CP), 32.2 d (3JPC = 5.8 Hz,
CH2CN), 42.8 s [CH(CH3)2], 48.8 d (2JPC = 30.2 Hz,
OCH2CH3), 72.9 d (1JPC = 201.6 Hz, CP), 172.8 d
(2JPC = 20.1 Hz, CNH). Mass spectrum, m/z (Irel, %):
247 (20.5), 232 (14.8), 218 (31.0), 207 (1.1), 155
(100), 144 (6.0), 104 (10.3), 91 (80.1), 77 (1.2), 65
(21.3), 41 (10.3). Found, %: C 53.58; H 9.11; N 5.50;
P 12.38. C11H22NO3P. Calculated, %: C 53.43; H 8.97;
N 5.66; P 12.53.
EXPERIMENTAL
1
The H, 13C, and 31P NMR spectra were recorded
from solutions in CDCl3 on a Varian Mercury 300
spectrometer at 300, 75.5, and 121.4 MHz, respec-
tively; the chemical shifts were measured relative to
TMS (1H, 13C) and H3PO4. The mass spectra (EI) were
recorded on an HP G1800A GCD GC/MS instrument
using a 30-m methyl silicone column.
Compounds 7b–7i were synthesized in a similar
way from compound 6 and the corresponding amine.
Diethyl [2-(propylamino)cyclobut-1-en-1-yl]-
1
phosphonate (7b). H NMR spectrum, δ, ppm: 0.84 t
Diethyl (4-chlorobut-1-yn-1-yl)phosphonate (6)
was prepared in our lab by refluxing but-3-yn-1-ol with
thionyl chloride. The product, 4-chlorobut-1-yne, was
isolated by distillation and dissolved in diethyl ether,
the solution was cooled to –78°C, an equivalent
amount of butyllithium was added, and the mixture
was allowed to gradually warm up to room temperature.
The mixture was then cooled again to –78°C, and
an equivalent amount of diethyl phosphorochloridate
was added. The reaction was quenched with 1 M
aqueous HCl, and the product was extracted into
diethyl ether, followed by evaporation of the solvent on
a rotary evaporator and distillation of the residue under
reduced pressure.
(3H, JHH = 8.4 Hz, CH2CH2CH3), 1.26 t (6H, JHH
=
7.5 Hz, OCH2CH3), 2.05 m (2H, CH2CH3), 2.40 br.t
and 2.61 br.t (2H each, JHH = 7.5 Hz, CH2CH2), 3.06 t
(2H, JHH = 6.5 Hz, NHCH2), 4.00 m (4H, OCH2CH3).
31P NMR spectrum: δP 28.83 ppm. 13C NMR spectrum,
δC, ppm: 11.44 s (CH2CH3), 15.9 d (3JPC = 6.6 Hz,
OCH2CH3), 20.3 s (CH2CH3), 20.5 s (CH2CH2), 43.9 s
(CH2N), 44.8 d (3JPC = 33.5 Hz, CH2CN), 60.2 d
(2JPC = 5.4 Hz, OCH2), 73.0 d (1JPC = 217.2 Hz, CP),
161.3 d (2JPC = 21.2 Hz, CN). Mass spectrum, m/z
(Irel, %): 247 (4.2), 232 (10.2), 207 (11.1), 158 (100),
144 (6.0), 133 (21.7), 104 (10.8), 85 (5.7), 43 (35.6).
Found, %: C 53.66; H 9.06; N 5.54; P 12.39.
C11H22NO3P. Calculated, %: C 53.43; H 8.97; N 5.66;
P 12.53.
Diethyl [2-(propan-2-ylamino)cyclobut-1-en-1-
yl]phosphonate (7a). Diethyl (4-chlorobut-1-yn-1-yl)-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020

AL QUNTAR et al.
140
Diethyl [2-(tert-butylamino)cyclobut-1-en-1-yl]-
phosphonate (7c). H NMR spectrum, δ, ppm: 1.20 s
2.70 br.t (2H, JHH = 6.5 Hz, CH2CH2), 2.88 br.t
(2H, JHH = 6.3 Hz, CH2CH2), 4.11 m (4H, OCH2CH3).
31P NMR spectrum: δP 27.85 ppm. 13C NMR spectrum,
δC, ppm: 15.9 d (3JPC = 6.2 Hz, OCH2CH3), 25.7 s
(CH2CH2), 33.6 d (3JPC = 5.6 Hz, CH2CH2), 39.4 s
(NCH3), 62.1 d (2JPC = 6.4 Hz, OCH2CH3), 68.9 d
(1JPC = 205.2 Hz, CP), 200.3 d (2JPC = 20.1 Hz, CN).
Mass spectrum, m/z (Irel, %): 219 (8.5), 206 (2.1), 133
(15.1), 132 (100), 172 (50.5), 144 (6.0), 104 (10.3),
91 (80.1), 77 (1.2), 65 (21.3), 41 (10.3). Found, %:
C 49.68; H 8.38; N 6.25; P 13.94. C9H18NO3P. Cal-
culated, %: C 49.31; H 8.28; N 6.39; P 14.13.
1
(9H, t-Bu), 1.26 t (6H, JHH = 6.7 Hz, OCH2CH3),
2.74 br.t (2H, JHH = 6.5 Hz, CH2CH2), 2.93 br.t (2H,
JHH = 6.3 Hz, CH2CH2), 3.96 m (4H, OCH2CH3).
31P NMR spectrum: δP 27.44 ppm. 13C NMR spectrum,
δC, ppm: 16.3 d (3JPC = 6.0 Hz, OCH2CH3), 23.4 s
(CH2CH2), 28.9 s [C(CH3)], 32.4 d (3JPC = 5.7 Hz,
CH2CN), 50.4 s [C(CH3)], 61.3 d (2JPC = 4.6 Hz,
OCH2CH3), 72.2 d (1JPC = 215.6 Hz, CP), 159.8 d
(2JPC = 19.6 Hz, CN). Mass spectrum, m/z (Irel, %): 261
(34.5), 246 (66.5), 233 (6.7), 218 (17.6), 206 (50.7),
178 (22.7), 160 (31.7), 132 (35.6), 108 (29.3), 95
(55.9), 69 (100), 57 (29.9). Found, %: C 54.97; H 9.17;
N 5.51; P 11.98. C12H24NO3P. Calculated, %: C 55.16;
H 9.26; N 5.36; P 11.85.
Diethyl {2-[(2-phenylethyl)amino]cyclobut-1-en-
1
1-yl}phosphonate (7g). H NMR spectrum, δ, ppm:
1.26 t (6H, JHH = 6.9 Hz, OCH2CH3), 2.68 br.t (2H,
JHH = 6.3 Hz, CH2CH2), 2.74 br.t (2H, JHH = 6.7 Hz,
CH2CH2), 2.81 br.t (2H, JHH = 6.5 Hz, CH2CH2Ph),
2.92 br.t (2H, JHH = 6.9 Hz, CH2CH2Ph), 3.96 m (4H,
OCH2CH3), 7.10–7.30 m (5H, Ph). 31P NMR spectrum:
δP 27.50 ppm. 13C NMR spectrum, δC, ppm: 16.1 d
(3JPC = 6.8 Hz, OCH2CH3), 27.7 s (CH2CH2), 38.5 d
(3JPC = 4.6 Hz, CH2CH2), 38.5 s (CH2CH2Ph), 42.7 s
(CH2CH2Ph), 60.4 d (2JPC = 5.7 Hz, OCH2CH3), 70.2 d
(1JPC = 216.6 Hz, CP), 126.0 (Carom), 128.2 (Carom),
128.5 (Carom), 139.0 (Carom), 160.8 d (2JPC = 19.6 Hz,
CN). Mass spectrum, m/z (Irel, %): 309 (0.5), 297 (1.1),
252 (29.2), 206 (100), 178 (17.2), 160 (29.1), 132
(2.1), 105 (11.5), 104 (11.4), 91 (12.0), 77 (5.2),
57 (1.0). Found, %: C 61.94; H 7.98; N 4.67;
P 9.88. C16H24NO3P. Calculated, %: C 62.12; H 7.82;
N 4.53; P 10.01.
Diethyl [2-(benzylamino)cyclobut-1-en-1-yl]-
1
phosphonate (7d). H NMR spectrum, δ, ppm: 1.26 t
(6H, JHH = 6.2 Hz, OCH2CH3), 2.82 br.t and 2.92 br.t
(2H each, JHH = 6.9 Hz, CH2CH2), 3.89 s (2H, CH2Ph),
3.96 m (4H, OCH2CH3), 7.27–7.34 m (5H, Ph).
31P NMR spectrum: δP 28.1 ppm. 13C NMR spectrum,
δC, ppm: 15.9 d (3JPC = 6.2 Hz, OCH2CH3), 21.8 s
(CH2CH2), 45.6 s (CH2Ph), 47.1 d (3JPC = 31.7 Hz,
CH2CH2), 60.2 d (2JPC = 7.8 Hz, OCH2CH3), 71.8 d
(1JPC = 215.6 Hz, CP), 126.6 (Carom), 127.3 (Carom),
128.2 (Carom), 141.3 (Carom), 162.4 d (2JPC = 19.2 Hz,
CN). Mass spectrum, m/z (Irel, %): 295 (3.9), 280
(22.1), 207 (5.3), 208 (100), 155 (3.8), 137 (8.6), 91
(70.8), 77 (18.8), 57 (13.5), 41 (15.5). Found, %:
C 60.88; H 7.44; N 4.83; P 10.61. C15H22NO3P.
Calculated, %: C 61.01; H 7.51; N 4.74; P 10.49.
Diethyl {2-[(2-hydroxyethyl)amino]cyclobut-1-
1
Diethyl (2-anilinocyclobut-1-en-1-yl)phospho-
en-1-yl}phosphonate (7h). H NMR spectrum, δ,
1
nate (7e). H NMR spectrum, δ, ppm: 1.24 t (6H,
ppm: 1.22 t (6H, JHH = 7.3 Hz, JPH = 1.3 Hz,
OCH2CH3), 2.38 br.t (2H, JHH = 7.5 Hz, CH2CH2),
2.57 br.t (2H, JHH = 7.5 Hz, CH2CH2), 3.16 t (2H,
JHH = 7.7 Hz, CH2CH2OH), 3.28 t (2H, JHH = 7.7 Hz,
CH2CH2OH), 4.06 m (4H, OCH2CH3). 31P NMR
spectrum: δP 27.98 ppm. 13C NMR spectrum, δC, ppm:
16.5 d (3JPC = 6.6 Hz, OCH2CH3), 22.7 s (CH2CH2),
45.6 d (3JPC = 31.1 Hz, CH2CH2), 48.5 s (CH2CH2OH),
54.0 s (CH2CH2OH), 60.4 d (2JPC = 5.2 Hz,
OCH2CH3), 73.8 d (1JPC = 211.6 Hz, CP), 160.6 d
(2JPC = 21.6 Hz, CN). Mass spectrum, m/z (Irel, %): 249
(2.2), 234 (8.4), 263 (15.6), 205 (13.8), 176 (10.3), 144
(100), 133 (21.7), 128 (50.5), 97 (33.5), 44 (28.4).
Found, %: C 47.00; H 7.95; N 5.73; P 12.59.
C10H20NO4P. Calculated, %: C 48.19; H 8.09; N 5.62;
P 12.43.
JHH = 7.2 Hz, OCH2CH3), 2.18 br.t (2H, JHH = 6.9 Hz,
CH2CH2), 2.81 br.t (2H, JHH = 6.5 Hz, CH2CH2),
3.96 m (4H, OCH2CH3), 7.17–7.32 (5H, Ph). 31P NMR
spectrum: δP 31.27 ppm. 13C NMR spectrum, δC, ppm:
16.0 d (3JPC = 6.0 Hz, OCH2CH3), 23.4 s (CH2CH2),
46.4 d (3JPC = 31.7 Hz, CH2CH2), 61.3 d (2JPC
=
6.2 Hz, OCH2CH3), 70.2 d (1JPC = 205.6 Hz, CP),
126.0 (Carom), 128.3 (Carom), 140.3 (Carom), 160.2 d
(2JPC = 18.8 Hz, CN). Mass spectrum, m/z (Irel, %):
281 (6.3), 264 (12.4), 207 (1.1), 168 (100), 144 (5.8),
135 (23.7), 91 (78.5), 77 (15.4), 65 (17.7), 41 (18.9).
Found, %: C 59.91; H 7.26; N 4.83; P 10.87.
C14H20NO3P. Calculated, %: C 59.78; H 7.17; N 4.98;
P 11.01.
Diethyl [2-(methylamino)cyclobut-1-en-1-yl]-
1
phosphonate (7f). H NMR spectrum, δ, ppm: 1.25 t
Diethyl {2-[di(propan-2-yl)amino]cyclobut-1-en-
1
(6H, JHH = 7.2 Hz, OCH2CH3), 2.52 s (3H, CH3),
1-yl}phosphonate (7i). H NMR spectrum, δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020

FACILE SYNTHESIS OF 2-AMINOCYCLOBUTENYLPHOSPHONATES
141
5. Bozkaya, U. and Özkan, İ., J. Org. Chem., 2012, vol. 77,
p. 5714.
1.14 d [12H, JHH = 6.2 Hz, CH(CH3)2], 1.26 t (6H,
JHH = 6.9 Hz, OCH2CH3), 2.68 br.t and 2.91 br.t (2H
each, JHH = 7.2 Hz, CH2CH2), 2.90 m [2H, CH(CH3)2],
4.09 m (4H, OCH2CH3). 31P NMR spectrum:
δP 30.32 ppm. 13C NMR spectrum, δC, ppm: 16.4 d
(3JPC = 6.2 Hz, OCH2CH3), 22.6 s [CH(CH3)2], 23.3 s
(CH2CH2), 32.7 d (3JPC = 5.6 Hz, CH2CH2), 48.8 s
[CH(CH3)2], 60.1 d (2JPC = 5.2 Hz, OCH2CH3), 73.3 d
(1JPC = 200.8 Hz, CP), 168.6 d (2JPC = 19.9 Hz, CN).
Mass spectrum, m/z (Irel, %): 289 (18.8), 274 (22.4),
259 (15.4), 246 (100), 231 (15.4), 218 (33.4), 207
(8.8), 188 (39.8), 155 (70.5), 144 (5.8), 76 (9.3), 41
(15.7). Found, %: C 57.96; H 9.66; N 4.94; P 10.8.
C14H28NO3P. Calculated, %: C 58.11; H 9.75; N 4.84;
P 10.70.
https://doi.org/10.1021/jo300877w
6. Kitayama, T., Kawauchi, T., Nakamura, M., Sufi, B.,
Padias, A.B., and Hall, H.K., Polymer, 2004, vol. 45,
p. 5085.
https://doi.org/10.1016/j.polymer.2004.05.024
7. Chen, X.P., Sufi, B.A., Padias, A.B., and Hall, H.K.,
Macromolecules, 2002, vol. 35, p. 4277.
https://doi.org/10.1021/ma012104f
8. Perrott, M.G. and Novak, B.M., Macromolecules, 1996,
vol. 29, p. 1817.
https://doi.org/10.1021/ma951516j
9. Wu, Z. and Grubbs, R.H., Macromolecules, 1995,
vol. 28, p. 3502.
https://doi.org/10.1021/ma00114a002
10. Casey, P.K. and Mathias, L.J., Polym. Commun., 1991,
Diethyl [2-(propylamino)cyclobutyl]phosphonate
vol. 32, p. 27.
1
(8). H NMR spectrum, δ, ppm: 0.88 t (3H, JHH
=
11. Hall, H.K. and Padias, A.B., J. Polym. Sci., Part A-1:
Polym. Chem., 2003, vol. 41, p. 625.
https://doi.org/10.1002/pola.10618
12. Ingham, S., Turner, R.W., and Wallace, T.W., J. Chem.
Soc., Chem. Commun., 1985, p. 1664.
7.5 Hz), 1.31 t (6H, JHH = 7.2 Hz), 1.60 m (2H), 1.92–
2.40 m (5H), 2.55 br.t (2H, JHH = 7.3 Hz), 2.95 m
(1H), 4.10 m (4H, OCH2CH3). 31P NMR spectrum:
δP 32.66 ppm. 13C NMR spectrum, δC, ppm: 11.4,
16.0 d (3JPC = 6.3 Hz), 18.1, 21.6, 27.8, 51.2, 42.7 d
(1JPC = 215.6 Hz), 54, 61.2 d (2JPC = 4.6 Hz). Mass
spectrum, m/z (Irel, %): 247 (4.2), 232 (10.2), 207
(11.1), 158 (100), 144 (6.0), 133 (21.7), 104 (10.8), 85
(5.7), 43 (35.6). Found, %: C 53.66; H 9.06; N 5.54;
P 12.39. C11H22NO3P. Calculated, %: C 53.43; H 8.97;
N 5.66; P 12.53.
https://doi.org/10.1039/C39850001664
13. Binns, F., Hayes, R., Ingham, S., Saengchantara, S.T.,
Turner, R.W., and Wallace, T.W., Tetrahedron, 1992,
vol. 48, p. 515.
https://doi.org/10.1016/S0040-4020(01)89013-X
14. Hayes, R., Ingham, S., Saengchantara, S.T., and
Wallace, T.W., Tetrahedron Lett., 1991, vol. 32, p. 2953.
https://doi.org/10.1016/0040-4039(91)80660-x
15. Binns, F., Hayes, R., Hodgetts, K.J., Saengchantara, S.T.,
Wallace, T.W., and Wallis, C.J., Tetrahedron, 1996,
vol. 52, p. 3631.
FUNDING
This research was supported by Al-Quds University
funding.
https://doi.org/10.1016/0040-4020(96)00039-7
16. Hodgetts, K.J., Saengchantara, S.T., Wallis, C.J., and
Wallace, T.W., Tetrahedron Lett., 1993, vol. 34, p. 6321.
https://doi.org/10.1016/s0040-4039(00)73742-7
17. Gourdel-Martin, M.E. and Huet, F., Tetrahedron Lett.,
1996, vol. 37, p. 7745.
CONFLICT OF INTEREST
The authors declare no conflict of interest.
REFERENCES
https://doi.org/10.1016/0040-4039(96)01763-7
18. Youcef, R.A., Boucheron, C., Guillarme, S., Legoupy, S.,
Dubreuil, D., and Huet, F., Synthesis, 2006, p. 633.
https://doi.org/10.1055/s-2006-926303
1. Moore, H.W. and Decker, O.H.W., Chem. Rev., 1986,
vol. 86, p. 821.
19. Dembitsky, V.M., J. Nat. Med., 2008, vol. 62, p. 1.
https://doi.org/10.1021/cr00075a006
https://doi.org/10.1007/s11418-007-0166-3
2. Misale, A., Niyomchon, S., and Maulide, N., Acc. Chem.
Res., 2016, vol. 49, p. 2444.
20. Hansen, T.V. and Stenstrøm, Y., Organic Synthesis:
Theory and Applications, Amsterdam: Elsevier, 1996,
vol. 5, p. 1.
https://doi.org/10.1021/acs.accounts.6b00375
https://doi.org/10.1016/s1047-773x(01)80002-0
21. Zarghi, A. and Arfaei, S., Iran. J. Pharm. Res., 2011,
3. Namyslo, J.C. and Kaufmann, D.E., Chem. Rev., 2003,
vol. 103, p. 1485.
https://doi.org/10.1021/cr010010y
vol. 10, p. 655.
4. Yavari, I. and Asghari, S., Tetrahedron, 1999, vol. 55,
p. 11853.
22. Talley, J.J., Prog. Med. Chem. Res., 1999, vol. 36,
p. 201.
https://doi.org/10.1016/S0040-4020(99)00671-7
https://doi.org/10.1016/s0079-6468(08)70048-1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020

AL QUNTAR et al.
142
23. Praveen, P.N., Rao, E.E., and Knaus, J., J. Pharm.
Pharm. Sci., 2008, vol. 11, p. 81.
37. López-Carrillo, V. and Echavarren, A.M., J. Am. Chem.
Soc., 2010, vol. 132, p. 9292.
https://doi.org/10.18433/j3t886
https://doi.org/10.1021/ja104177w
24. Smith, S.C., Clarke, E.D., Ridley, S.M., Bartlett, D.,
Greenhow, D.T., Glithro, H., Klong, A.Y., Mitchell, G.,
and Mullier, G.W., Pest Manage. Sci., 2005, vol. 61,
p. 16.
38. Negishi E., Liu F., Choueiry D., and Mohamud M.M.,
J. Org. Chem., 1996, vol. 61, p. 8325.
https://doi.org/10.1021/jo961277d
39. Perri, S.T., Dyke, H.K., and Moore, H.W., J. Org. Chem.,
1989, vol. 54, p. 2032.
https://doi.org/10.1021/jo00270a004
40. Song, Z.Q., Li, Y.X., Liu, M., Cong, L.Q., and Liu, Y.H.,
Organometallics, 2006, vol. 25, p. 5035.
https://doi.org/10.1021/om060505j
41. Chen, C., Xi, C., Lai, C., Wang, R., and Hong, X., Eur. J.
Org. Chem., 2004, p. 647.
https://doi.org/10.1002/ps.980
25. Liu, Z.Y., Wang, Y.M., Han, Y.X., Liu, L., Jin, J., Yi, H.,
Li, Z.R., Jiang, J.D., and Boykin, D., Eur. J. Med. Chem.,
2013, vol. 65, p. 187.
https://doi.org/10.1016/j.ejmech.2013.04.046
26. Ortuño, R., Moglioni, M., and Moltrasio, A.G., Curr.
Org. Chem., 2005, vol. 9, p. 237.
https://doi.org/10.2174/1385272053369088
27. Sergeiko, A., Poroikov, V., Hanuš, L., and Dembitsky, V.,
Open Med. Chem. J., 2008, vol. 2, p. 26.
https://doi.org/10.2174/1874104500802010026
28. Owsley, D.C. and Bloomfield, J.J., J. Chem. Soc. C,
1971, p. 3445.
https://doi.org/10.1039/j39710003445
29. Kosugi, H., Sekiguchi, S., Sekita, R., and Uda, H., Bull.
Chem. Soc. Jpn., 1976, vol. 7, p. 520.
https://doi.org/10.1002/chin.197620094
30. Baldwin, S.W., Organic Photochemistry, Padwa A., Ed.,
New York: Marcel Dekker, 1981, vol. 5, p. 123.
31. Demuth, M., and Gamal, M., Synthesis, 1989, p. 145.
https://doi.org/10.1002/ejoc.200300485
42. Al Quntar, A.A., Srebnik, M., Terent’ev, A.O., and
Dembitsky, V., Mini-Rev. Org. Chem., 2014, vol. 11,
p. 445.
https://doi.org/10.2174/1570193x1104140926170132
43. Bauer, G. and Haegele, G., Z. Naturforsch., B: Anorg.
Chem., Org. Chem., 1979, vol. 34, p. 1252.
https://doi.org/10.1515/znb-1979-0918
44. Ueda, T., Inukai, K., and Muramatsu, H., Bull. Chem.
Soc. Jpn., 1969, vol. 42, p. 1684.
https://doi.org/10.1246/bcsj.42.1684
45. Tomioka, H., Watanabe, M., Kobayashi, N., and
Hirai, K., Tetrahedron Lett., 1990, vol. 31, p. 5061.
https://doi.org/10.1016/s0040-4039(00)97806-7
46. Facklam, T., Hoffmann, K.L., and Regitz, M., Chem.
Ber., 1987, vol. 120, p. 1397.
https://doi.org/10.1055/s-1989-27181
32. Alibés, R., March, P., Figueredo, M., Font, J.,
Racamonde, M., Rustullet, A., Alvarez-Larena, A.,
Piniella, J.F., and Parella, T., Tetrahedron Lett., 2003,
vol. 44, p. 69.
https://doi.org/10.1002/cber.19871200817
47. Andriamiadanarivo, R., Pujol, B., Chantegrel, B.,
Dehayes, C., and Doutheau, A., Tetrahedron Lett., 1993,
vol. 34, p. 7923.
https://doi.org/10.1016/s0040-4039(02)02528-5
33. Delas, C., Urabe, H., and Sato, F., Tetrahedron Lett.,
2001, vol. 42, p. 4147.
https://doi.org/10.1016/s0040-4039(00)61512-5
https://doi.org/10.1016/s0040-4039(01)00666-9
48. Darling, S.D. and Subramanian, N., Tetrahedron Lett.,
1975, vol. 38, p. 3279.
34. Brandsma, L., Spek, A.L., Trofimov, B.A., Tara-
sova, O.A., Nedolya, N.A., Afonin, A.V., and Zin-
shenko, S.V., Tetrahedron Lett., 2001, vol. 42, p. 4687.
https://doi.org/10.1016/s0040-4039(01)00787-0
35. Barbero, A., Cuadrado, P., Garcıa, C.A., Rincon, J.A.,
and Pulido, F.J., J. Org. Chem., 1998, vol. 63, p. 7531.
https://doi.org/10.1021/jo980874s
https://doi.org/10.1016/s0040-4039(00)91425-4
49. Sinelnikove, Y., Rubinstein, A., Srebnik, M., and Al
Quntar, A.A., Tetrahedron Lett., 2009, vol. 50, p. 867.
https://doi.org/10.1016/j.tetlet.2008.11.108
50. Srivastava, H.K., Al Quntar, A.A., Azab, A.,
Srebnik, M., and Shurki, A., Tetrahedron, 2009, vol. 65,
p. 4389.
36. Liu, Y., Liu, M., and Song, Z., J. Am. Chem. Soc., 2005,
vol. 127, p. 3662.
https://doi.org/10.1021/ja042636m
https://doi.org/10.1016/j.tet.2009.03.053
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 1 2020