Some Transformations of Mono-and Dichloro(diethoxyphosphoryl)acetaldehydes

Article abstract of DOI:10.1134/S1070363220010132

Addition of ethanol and diethyl phosphonate to the carbonyl group of 2,2-dichloro-2-(diethoxyphosphoryl)-acetaldehyde has been studied, and the corresponding α-chloro ether, acetal, and phosphorylated metrifonate have been obtained. α,α-Dichloro-α-phospho

Full text of DOI:10.1134/S1070363220010132

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 1, pp. 89–92. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 1, pp. 117–121.
Some Transformations of Mono-
and Dichloro(diethoxyphosphoryl)acetaldehydes
a
b
a
a
a,
V. M. Ismailov , G. E. Allakhverdieva , N. D. Sadykhova , I. A. Mamedov , and N. N. Yusubov *
a
Baku State University, Baku, AZ 1148 Azerbaijan
b
Gyandzha State University, Gyandzha, AZ 2001 Azerbaijan
*
e-mail: yniftali@gmail.ru
Received December 28, 2018; revised November 13, 2019; accepted November 15, 2019
Abstract—Addition of ethanol and diethyl phosphonate to the carbonyl group of 2,2-dichloro-2-(diethoxyphosphoryl)-
acetaldehyde has been studied, and the corresponding α-chloro ether, acetal, and phosphorylated metrifonate have
been obtained. α,α-Dichloro-α-phosphoryl carbonyl compounds have been found to undergo haloform cleavage
by the action of bases. Perkow reaction of mono- and dichloro(diethoxyphosphoryl)acetaldehydes with triethyl
phosphite afforded diethyl 2-(diethoxyphosphoryl)ethenyl phosphates.
Keywords: (diethoxyphosphoryl)acetaldehyde, alkoxyvinylphosphonates, haloform type cleavage, chloro ethers,
acetals, metrifonate
DOI: 10.1134/S1070363220010132
α-Phosphorylated aldehydes are convenient starting
materials for solving fundamental problems of organo-
phosphorus chemistry. In recent time, halo-substituted
α-phosphorylated aldehydes have attracted much atten-
tion since the presence of halogen atoms in aldehyde
molecules gives rise to additional coordination sites
and opens synthetic routes to various organophosphorus
compounds.
50°C, compound 3 decomposed into the initial aldehyde
and ethanol. The structure of 3 was confirmed by the
IR spectrum which lacked carbonyl stretching band but
contained νOH band at 3300–3600 cm , as well as by
some chemical transformations (Scheme 1). In particu-
lar, treatment of 3 with thionyl chloride on cooling gave
diethyl 1,1,2-trichloro-2-ethoxyethylphosphonate (4) as
a result of substitution of the hydroxy group by chlorine.
Compound 4 was stable even on prolonged heating (120–
–
1
2
-Chloro-2-(diethoxyphosphoryl)acetaldehyde has
150°C, 2 h). The acylation of 3 with acetyl chloride in the
been synthesized in a low yield by reaction of chloro-
methylphosphonate with ethyl formate in the presence
of metallic sodium [1]. Asimple preparative synthesis of
mono- and dichloro(diethoxyphosphoryl)acetaldehydes 1
and 2 by low-temperature chlorination of (diethoxyphos-
phoryl)acetaldehyde with molecular chlorine was later
reported in [2, 3]. Recent systematic studies of phosphory-
lated monochloro aldehydes made it possible to obtain a
number of heterocyclic systems that are difficult to access
by other methods [4–6]. Acetaldehydes 1 and 2 can be
regarded as phosphorylated chloral derivatives, and study
of their reactivity is important for organic synthesis.
presence of triethylamine furnished acetate 5. α-Chloro
ether 4 was also synthesized independently by passing
molecular chlorine through 2-ethoxyethenylphosphonic
dichloride heated to 120°C; this reaction involved suc-
cessive chlorination of the double bond, dehydrochlo-
rination, and further chlorination with the formation of
1,1,2-trichloro-2-ethoxyethylphosphonic dichloride (6),
and alcoholysis of the latter in the presence of a tertiary
amine afforded phosphonate 4 (Scheme 2). It should be
noted that compounds 4 and 5 exhibit enhanced fibrino-
lytic activity.
Herein we report some transformations of aldehydes
and 2 in reactions with ethanol, ethanolic sodium hy-
droxide, diethyl phosphonate, triethyl phosphite, and dry
sodium ethoxide, which involved the carbonyl group of
the substrate.
Phosphorylated dichloroacetaldehyde 2 readily re-
acted with diethyl phosphonate (Abramov reaction) to
afford hydroxy bis-phosphonate 7 (Scheme 3); the latter
can be regarded as phosphorylated metrifonate derivative
which may be used as insecticide in agriculture.
1
α
β
Aldehyde 2 readily adds ethanol to give hemiacetal
Haloform type cleavage of the C –C bond of alde-
3
which is stable at room temperature; on heating above
hyde 2 by the action of ethanolic sodium hydroxide or
8
9

90
ISMAILOV et al.
Scheme 1.
O
O
H
O
C H OH
2
5
(
C H O) PC(Cl) C
2
5
2
2
(C H O) PC(Cl) CHOEt
2
5
2
2
OH
2
3
O
SOCl2
NEt3
(
C H O) PC(Cl) CHOEt
2 5 2 2
4
Cl
O
CH COCl
(C H O) PC(Cl) CHOEt
2 5 2 2
3
NEt3
OCOCH3
5
Scheme 2.
O
O
O
Cl , 120qC
2
Cl PꢀCHꢀCHꢀOEt
Cl PꢀC=CHꢀOEt
2
Cl PꢀCH=CHꢀOEt
2
2
ꢀ
HCl
Cl
Cl Cl
O
Cl
O
Cl2
2EtOH
Et N
Cl PꢀCCl CH
(C H O) PꢀCClꢀCHꢀOEt
2 5 2
2
2
2
3
OEt
Cl
6
4
Scheme 3.
O
O
H
(
EtO) PHO
2
(
EtO) PCCl C
(EtO) PCCl CHꢀP(OEt)
2 2 2
2
2
O
O
OH
2
7
morpholine produced diethyl (dichloromethyl)phospho-
nate (8). In the reaction with morpholine, morpholine-
Thus, the chemical reactivity of chlorinated (diethoxy-
phosphoryl)acetaldehydes 1 and 2 is similar to the reac-
tivity of trichloroacetaldehyde. They add nucleophiles
at the carbonyl group, undergo haloform type cleavage,
and react with trialkyl phosphites according to Perkow.
Cleavage of the P–C bond with the formation of triethyl
phosphate was observed in the reaction with solid sodium
ethoxide.
4-carbaldehyde was also formed (Scheme 4). In contrast,
the reaction of 2 with solid sodium ethoxide in boiling di-
ethyl ether (heterogeneous conditions) involved cleavage
of the P–C bond with the formation of triethyl phosphate
(9) and sodium 2,2-dichloroethen-1-olate; treatment of
the latter with dilute aqueous HCl gave dichloroacetal-
dehyde (10) (Scheme 5).
EXPERIMENTAL
Like chloral, Perkow reaction of mono- and dichloro
aldehydes 1 and 2 with triethyl phosphite afforded
The H and 13C NMR spectra were recorded on a
Bruker-300 spectrometer at 300 and 75 Hz, respectively,
using hexamethyldisiloxane as internal standard. The IR
spectra were recorded in mineral oil on a Specord 75-IR
instrument.
1
2
-(diethoxyphosphoryl)ethenyl diethyl phosphates 11a
1
and 11b (Scheme 6). According to the H NMR data,
the C=C double bond in 11a has E configuration
3
(
JHH = 14.0 Hz).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

SOME TRANSFORMATIONS OF MONO- AND DICHLORO(DIETHOXYPHOSPHORYL)ACETALDEHYDES 91
Scheme 4.
GH = 7.85 ppm
Cl
O
Cl
C H OꢀP
2
5
HN
O
H
+
CꢀN
O
OC H5
8
2
O
O
P
C H O
2
5
Cl
O
C H O
2
5
O
Cl Cl
C H OꢀP
Cl
2
5
EtOH + NaOH
2
OC H5
2
8
Scheme 5.
O
C H ONa
H
O
2
5
HCl
(
EtO) PCCl C
HCCl C
2
2
2
(EtO) POC H + [CCl =CHONa]
2
2
5
2
Et O, 36qC
2
H
O
O
10
9
Scheme 6.
GP = 8.4 ppm
GP = ꢀ5.4 ppm
Cl
O
(
EtO) PC
+ (EtO)3P
(EtO) PC=CHOP(OEt)2
2
2
H
O
R
O
R
O
1, 2
ꢀꢀɚ, 11b
R = H (1, ꢀꢀɚ), Cl (2, 11b).
(1H, CH, 2JHP = 2.0). Found, %: Cl 23.54; P 10.55.
Diethyl (1,1,2-trichloro-2-ethoxyethyl)phosphonate
(4). A mixture of 10 g of aldehyde 2, 2.8 mL of ethanol,
C H Cl O P. Calculated, %: Cl 21.06; P 10.54.
1
0
19
2
6
5
g of triethylamine, and 50 mL of benzene was cooled
(1,1,2-Trichloro-2-ethoxyethyl)phosphonic dichlo-
to 0–5°C, and 3.2 g of thionyl chloride was added. The
mixture was stirred for 3 h at 30–40°C, the precipitate
was filtered off, and the filtrate was evaporated. Yield
ride (6). Dry chlorine was passed over a period of 2–3 h
through 10 g of 2-ethoxyethenylphosphonic dichloride
heated to 120°C. The mixture was then subjected to frac-
tional distillation. Yield 51%, bp 89–90°C (0.2 mmHg),
2
0
8
.2 g (58%), bp 105–108°C (0.5 mmHg), d = 1.3113,
4
2
0
1
n
= 1.4670. H NMR spectrum (CDCl ), δ, ppm (J,
1
D
3
mp 48°C. H NMR spectrum, δ, ppm (J, Hz): 1.22 t
Hz): 1.1–1.25 m (9H, CH ), 3.85–4.02 m (6H, OCH ),
3
3
2
(3H, CH , J = 6.9), 3.75 m (2H, CH O), 5.75 s (1H).
3 HH 2
5
.85 d (1H, CH, 2JHP = 2.0). Found, %: Cl 33.44; P 9.77.
Found, %: P 3.67; Cl 22.14. C H Cl PO . Calculated, %:
4 6 5 2
C H Cl O P. Calculated, %: Cl 33.97; P 9.89.
P 3.82; Cl 21.90.
8
16
3
4
2
,2-Dichloro-2-(diethoxyphosphoryl)-1-ethoxy-
ethyl acetate (5) was synthesized in a similar way from
5 g of aldehyde 2 and 6.6 g of acetyl chloride using
1 mLof ethanol and 6.7 g of pyridine. Yield 22 g (71%),
Alcoholysis of (1,1,2-trichloro-2-ethoxyethyl)-
phosphonic dichloride (6). Ethanol, 10 mL, was added
with vigorous stirring to a mixture of 5 g (0.02 mol) of
phosphonic dichloride 6 and 2.1 g (0.02 mol) of trieth-
ylamine in 100 mL of diethyl ether on cooling with ice
water. The mixture was stirred for 2 h at room temperature
and was then refluxed for 2 h. The precipitate of triethyl-
amine hydrochloride was filtered off, the solvent was
2
1
2
0
20
bp 120–121°C (0.5 mmHg), d = 1.2724, n = 1.4565.
H NMR spectrum (CDCl ), δ, ppm (J, Hz): 1.1 t (3H,
4
D
1
3
3
3
CH , J = 6.9), 1.25 t (6H, CH , J = 7.2), 2.1 s (3H,
3
HH
3
HH
CH CO), 3.75 m (2H, OCH ), 4.1 m (4H, OCH ), 5.95 d
3
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020

92
ISMAILOV et al.
removed from the filtrate, and the product (compound 4)
144–145°C (0.1 mmHg), nD20 = 1.4260. H NMR spec-
1
was isolated by fractional distillation. Yield 3.2 g (64%),
trum (CDCl ) δ, ppm (J, Hz): 1.15–1.25 m (12H, CH ,
3
3
2
0
20
bp 106–108°C (0.5 mmHg), d = 1.3134, n = 1.4657.
3JHH = 6.9), 4.01–4.20 m (8H, OCH ), 5.4 d.d (1H, PCH=,
4
D
2
Tetraethyl (1,1-dichloro-2-hydroxyethane-1,2-diyl)-
diphosphonate (7). Aldehyde 2, 6.2 g, was cooled to
–8°C, and 2.7 g of diethyl phosphate was added with
3JHH = 14.0, 2JHP = 10.0), 7.20 d.d.d (1H, =CHO, 3JHH
=
4.0, 3JHP = 6.5, 12.0). Found, %: C 37.68; H 10.12; P
1
1
1
5
9.76. C H O P . Calculated, %: C 37.97; H 9.96; P
1
0
22
7 2
stirring. The mixture was stirred for 3 h at 50–60°C, and
9.62.
1
was then evacuated at 60–80°C. Yield 5 g (70%). H
2
-Chloro-2-(diethoxyphosphoryl)ethenyl diethyl
NMR spectrum (CDCl ), δ, ppm (J, Hz): 1.15–1.25 m
3
(
12H, CH ), 3.95–4.15 m (8H, OCH ), 3.36 d (1H, PCH,
phosphate (11b) was synthesized in a similar way. Yield
7.9 g (82%), bp 147–148°C (0.1 mmHg), nD20 = 1.4480.
3
2
2
JHP = 18.0). Found, %: P16.21; Cl 18.62. C H Cl P O.
10
22
2 2
Calculated, %: P 16.02; Cl 18.33.
1
H NMR spectrum (CDCl ), δ, ppm (J, Hz): 1.25 t (6H,
3
Diethyl (dichloromethyl)phosphonate (8). a. Alde-
hyde 2, 10 g, was added to a solution of 1.6 g of sodium
hydroxide in 20 mL of ethanol. Evolution of heat was
observed, and a solid precipitated. The precipitate was
filtered off, the filtrate was evaporated, and the residue
was distilled under reduced pressure. Yield 7 g (88%),
3
3
CH , J = 7.2), 1.30 t (6H, CH , J = 7.1), 4.02 m (8H,
3
HH
3
HH
13
3
OCH ), 7.2 q (1H, CH=, J = 9.0). C NMR spectrum,
2
HP
1
δ , ppm (J, Hz): 82.6 (PC=, J = 158.0), 163.5 (=CO,
J = 20.0). Found, %: P17.54; Cl 10.23. C H ClO P .
Calculated, %: C 34.23; H 5.99; P 17.68; Cl 10.12.
C
CP
2
CP
10 21
7 2
2
0
20
1
bp 77–79°C(0.5 mmHg), d = 1.2808, n = 1.4520. H
4
D
CONFLICT OF INTEREST
NMR spectrum (CDCl ), δ, ppm (J, Hz): 1.5 t (6H, CH ,
3
3
3
3
JHH = 7.1), 4.3 m (4H, OCH , J = 7.1), 5.5 d (1H,
CH, 2JHP = 12.7). C NMR spectrum, δ , ppm: 16.61
2
HH
No conflict of interest was declared by the authors.
REFERENCES
13
C
(
CH ), 61.57 (CH), 65.39 (CH ). Found, %: P 14.21; Cl
3 2
3
1.65. C H Cl O P. Calculated, %: P 14.09; Cl 31.81.
5 11 2 3
1
2
. Ioffe, S.T., Vatsuro, K.V., Petrovskii, P.V., and Kabach-
nik, M.I., Izv. Akad. Nauk SSSR, Ser. Khim., 1971, no. 4,
p. 731.
b. Ethanol, 2.7 mL, was added to a mixture of 12 g of
aldehyde 2 and 30 mL of benzene, 5 mL of morpholine
was then added, and the mixture was stirred for 2 h at
4
was subjected to fractional distillation under reduced
pressure. Yield 13.7 (72%), bp 77–78°C (0.5 mmHg),
d
. Ismailov, V.M., Moskva, V.V., Dadashova, L.A., Zyko-
va, T.V., and Guseinov, F.I., Zh. Obshch. Khim., 1982,
vol. 52, no. 9, p. 2140.
0–60°C. The solvent was distilled off, and the residue
2
0
20
3. Ismailov, V.M., Moskva, V.V., and Zykova, T.V., Zh.
Obshch. Khim., 1983, vol. 53, no. 12, p. 2763.
= 1.2826, nD = 1.4511.
4
Reaction of aldehyde 2 with solid sodium ethoxide.
4
5
. Asadov, Kh.A., Burangulova, R.N., and Guseinov, F.I.,
Chem. Heterocycl. Compd., 2003, vol. 39, no. 5, p. 671.
https://doi.org/10.1023/A:1025118804568
Aldehyde 2, 23 g, was added to a mixture of 5 g of freshly
prepared sodium ethoxide in 20 mL of diethyl ether. The
mixture vigorously boiled up on heating to 34°C. The
precipitate was filtered off, and triethyl phosphate (9) was
. Asadov, Kh.A., Gurevich, P.A., Egorova, E.A., Burangu-
lova, R.N., and Guseinov, F.I., Chem. Heterocycl. Compd.,
2003, vol. 39, no. 11, p 1521.
isolated from the filtrate. Yield 19.6 g (70%), bp 50–51°C
(
1 mmHg), d 42 0 = 1.1007, nD = 1.4085 [7].
20
https://doi.org/10.1023/B:COHC.0000014418.16494.f8
. Asadov, Kh.A., Zh. Khim. Probl., 2018, no. 4, p. 601.
The precipitate was treated with dilute aqueous HCl
6
to obtain 4.9 g (41%) of dichloroacetic aldehyde (10), bp
20
7. Nifant’ev, E.E., Khimiya fosfororganicheskikh soedinenii
Chemistry of Organophosphorus Compounds), Moscow:
9
0–92°C, d 42 0 = 1.3740, nD = 1.4290 [8].
-(Diethoxyphosphoryl)ethenyl diethyl phosphate
11a). Triethyl phosphite, 3.5 g (0.02 mol), was added
with stirring to a mixture of 6.5 g (0.02 mol) of aldehyde
and 100 mL of dioxane cooled to 5–10°C. The mixture
was stirred for 1 h at room temperature and for 2–3 h at
0–80°C. The solvent was removed, and the residue was
distilled under reduced pressure. Yield 6.4 g (76%), bp
(
2
Mosk. Gos. Univ., 1971, p. 154.
(
8
. Jira, R., Kopp, E., McKusick, B., Röderer, G., Bosch, A.,
and Fleischeman, G., Ullmann’s Encyclopedia of Indus-
trial Chemistry, Weinheim: Wiley-VCH, 2012, vol. 8,
p. 685.
1
6
https://doi.org/10.1002/14356007.a06_527.pub2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020