SYNTHESIS OF ETHYL 4,5-BIS(DIETHOXYPHOSPHORYLMETHYL)-3-FUROATE
67
5
2
7
0.4, 2.6 Hz), 3.45 d.d (Р СН , J = 21.2, 2.0 Hz),
reaction time was 10 min. Triethyl phosphite and
diethyl ethanephosphonate were distilled in a vacuum
(1 mmHg) in the temperature range 30–65°C. The
residue was diphosphonate 7. Yield 7.8 g (98%), light
2
PH
2
.90 br.s (Н -furan); phosphate 10: 2.35 d (СН -furan,
JPH = 4.0 Hz), 3.21 d (2Н, СН Р, J = 21.2 Hz). С
NMR spectrum, δ , ppm: common signals: 16.33 br.s
СН -phosphonate, СН -phosphate), 61.97 d (СН О-phos-
3
13
2
PH
С
1
(
yellow syrup. Н NMR spectrum, δ, ppm: 1.13–1.33 m
3
3
2
2
4
phonate, J = 6.3 Hz), 62.32 d (СН О-phosphonate,
(9Н, СН -ethyl), 3.40 d.d (2Н, Р СН , J = 20.4,
PC
2
3
2
PH
2
3
5
JPC = 6.5 Hz), 119.09 (С -furan); diphosphonate 7:
2.4 Hz), 3.44 d.d (2Н, Р СН , J = 21.2, 2.0 Hz),
2 PH
4
1
1
2
1
4.25 (СН -ethyl), 20.60 d (Р СН , J = 140.7 Hz),
3.95–4.09 m (4Н, СН О–Р), 4.26 q (2Н, СН О–С,
2 2
3
2
PC
5
1
2
13
5.30 d (Р СН , J = 142.5 Hz), 60.22 (СН О-ester),
JHH = 7.2 Hz), 7.88 d (1Н, Н -furan, J = 2.4 Hz). С
2
PC
2
2
PH
4
3
12.50 t (С -furan, J = J = 9.5 Hz), 145.97 d.d
NMR spectrum, δ , ppm: 14.23 (СН -ethyl), 16.82 d
PC
PC
С
3
5
2
3
2
3
4
(
С -furan, J = 12.0 Hz, J = 9.1 Hz), 147.23 d (С -
furan, J = 2.0 Hz), 163.71 (С=О); phosphate 10:
2.23 (СН -furan), 13.96 (СН -ethyl), 21.75 (Р СН ,
JPC = 142.6 Hz), 61.11 (СН О-ester), 63.08 d (СН О-
phosphate, J = 5.3 Hz), 111.94 d (С -furan, J
.5 Hz), 148.38 (С -furan), 155.54 (С -furan), 162.53
(СН -phosphonate, J = 3.1 Hz), 20.58 d (Р СН ,
PC
PC
3 PC 2
3
1
5
1
JPC = 140.3 Hz), 25.29 d (Р СН , J = 142.2 Hz),
2 PC
PC
4
1
60.19 (СН О-ester), 61.96 d (СН О-phosphonate,
3
3
2
2
2
1
2
2
JPC = 6.1 Hz), 62.29 d (СН О-phosphonate, J
=
2
2
2
PC
2
4
2
4
2
3
=
5.9 Hz), 112.48 t (С -furan, J = J = 9.5 Hz),
119.07 br.s (С -furan), 145.95 t (С -furan, J = J
10.1 Hz), 147.19 br.s (С -furan, 163.07 (С=О).
NMR spectrum, δ , ppm: 26.56 d (Р ), 23.04 d (Р ),
PC
PC
PC PC
2
5
3
5
2
3
9
(
2
1
=
Р
PC
PC
31
3
1
2
С=О). Р NMR spectrum, δ , ppm: diphosphonate 7:
Р
4
5
5
4
5
6.60 d (Р ), 23.08 d (Р ), J 4 5 = 18.2 Hz; phosphate
P P
Р
4
2
5
0: 25.78 (Р ), 2.74 (Р ).
JP4P5 = 18.0 Hz.
Ethyl 4,5-bis-(diethoxyphosphorylmethyl)furan-
-carboxylate (7). a. The preparation obtained by
ACKNOWLEDGMENTS
The work was carried out within the frames of the
basic part of state project of the Ministry of education
and science of Russia.
3
bromination of phosphonate 4 with NBS, 4.0 g, was
mixed with 4 mL of triethyl phosphite, and the mixture
obtained was gradually heated with stirring to 175°C.
At 130°C distillation of ethyl bromide began which
completed at 170°C. Total reaction time was 10 min.
The fraction boiling in the range 30–55°C (1 mmHg)
was distilled off, and the residue was kept at this
residual pressure and the bath temperature 60–65°C for
REFERENCES
1
2
3
. Pevzner, L.M., Russ. J. Gen. Chem., 2015, vol. 85,
no. 2, p. 428. DOI: 10.1134/S1070363215020139.
3
(
0 min. Main component of the preparation obtained
. Pevzner, L.M., Russ. J. Gen. Chem., 2015, vol. 85,
no. 7, p. 1650. DOI: 10.1134/S1070363215070130.
1
3.8 g) was diphosphonate 7. Н NMR spectrum, δ,
4
ppm: 1.18–1.34 m (СН -ethyl), 3.38 br.d (Р СН , J =
3
2
PH
. Sadykov, A.S. and Aslanov, Kh.A., Alkaloidy khino-
lozidinovogo ryada (The Alkaloids of Quinolizidine
Series), Moscow: Nauka, 1975, p. 30.
5
2
0.8 Hz), 3.41 br.d (Р СН , J = 20.8 Hz), 3.98–4.06
2 PH
m (СН О–Р), 4.19-4.32 m (СН О–С), 7.86 br.s (Н -
furan). С NMR spectrum, δ , ppm: 14.11 (СН -
ethyl), 16.37 br.s (СН -phosphonate), 20.54 d (Р СН ,
2
2
2
1
3
С
3
4
5
6
. Elyakov, G.B. and Stonik, V.A., Terpenoidy morskikh
organizmov (Terpenoids of Sea Organisms), Moscow:
Nauka, 1986.
4
3
2
1
5
1
JPC = 140.3 Hz), 25.24 d (Р СН , J = 141.7 Hz),
2
PC
6
0.22 (СН О-ester), 62.01 d (СН О-phosphonate,
2
2
. Ohana, P., Delmer, D.P., Steffens, J.C., Matthews, D.E.,
Mayer, R., and Benziman, M., J. Biol. Chem., 1991,
vol. 266, no. 21, p. 13742.
2
2
JPC = 6.6 Hz), 62.34 d (СН О-phosphonate, J
=
2
PC
4
2
3
6
.5 Hz), 112.44 t (С -furan, J = J = 9.6 Hz),
PC PC
3
5
2
1
19.04 (С -furan), 145.91 d.d (С -furan, J = 11.8 Hz,
PC
. Niva, T., Asada, H., Tsutsui, S., and Miyazaki, T., Am.
J. Nephrol., 1995, vol. 15, no. 6, p. 463. DOI:
10.1159/000168887.
3
2
3
JPC = 9.9 Hz), 147.21 d (С -furan, J = 2.2 Hz),
PC
3
1
1
(
63.05 (С=О). Р NMR spectrum, δ , ppm: 26.54 d
Р ), 23.02 d (Р ), J 4 5 = 18.1 Hz.
Р
4
5
5
P P
7. Pevzner, L.M., Russ. J. Gen. Chem., 2012, vol. 82,
no. 3, p. 404. DOI: 10.1134/S1070363212030073.
b. The mixture of 8.7 g of iodide 11 and 6 mL of
triethyl phosphite was gradually heated under the
intense stirring. Distillation of ethyl iodide began at
0°C and completed at 165°C. The reaction mixture
formed was heated to 170°C and then cooled. Total
8
9
. Mnjoyan, A.L. and Aroyan, A.A., Dokl. Аkad. Nauk
Аrm. SSR, 1958, vol. 27, p. 101.
. Pevzner, L.M., Russ. J. Gen. Chem., 2006, vol. 76,
no. 4, p. 621. DOI: 10.1134/S1070363206040207.
9
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016