SYNTHESIS OF 2-AMINO-5-HYDROXY-5-PHOSPHONOVALERIC ACID
1917
3
δ, ppm: 1.24 t (3Н, СН , J = 7.0 Hz), 1.29 t (6Н,
system equipped with DAD, ELSD and a single-
quadrupole mass-selective detector in electrospray
ionization mode.
3
HH
3
СН , J = 7.0 Hz), 1.67–1.85 m (2H, CH ), 1.87–
.10 m (2H, CH ), 2.00 s (3H, Ac), 3.77–3.92 m (1Н,
3
HH
2
2
2
СНО), 4.02–4.24 m (6Н, СН О), 4.47–4.65 m (1Н,
2
3
13
СНN), 6.63 br. d (1Н, NH, J = 7.6 Hz). С NMR
ACKNOWLEDGMENTS
HH
spectrum (CDCl ), δ , ppm (the spectral data for the
minor isomer are indicated by asterisk): 14.01, 16.33 d
3
С
The author thanks A.V. Afanasiev (OOO
“Chembridge”) for the chromatography-mass spectral
analysis of new organophosphorus compounds.
3
(
JРC = 5.8 Hz), 22.78* [СН С(О)], 22.84 [СН С(О)],
3 3
2
2
2
7.07 d ( J = 1.9 Hz), 27.17* d ( J = 1.9 Hz), 28.12* d
РC РC
JРC = 14.6 Hz), 28.77 d ( J = 14.6 Hz), 51.91
3
3
(
(
(
(
РC
This work was supported by the Russian
Foundation for Basic Research (grant no. 18-03-
CHN), 61.28* [C(O)OC], 61.33 [C(O)OC], 62.62 d
2
1
1
JРC = 7.3 Hz), 66.73* d ( J = 163.3 Hz), 67.17 d
РC
0
0959) and the Ministry of Education and Science of
JРC = 163.3 Hz), 170.4 [C(O)CH ], 172.26 [C(O)O],
3
the Russian Federation in the frame of the
governmental task (no. 0090-2017-0024).
3
1
1
2
72.41 [C(O)O]. Р NMR spectrum (CDCl ), δ , ppm:
5.58, 25.77*. Mass spectrum (LCМS), m/z: 340.3
3 P
+
[
M + H] (calculated for C H NO P: 339.3). Found
13 26 7
CONFLICT OF INTERESTS
No conflict of interests was declared by the author.
REFERENCES
P, %: 8.96, 8.82. C H NO P. Calculated P, %: 9.13.
13
26
7
2
-Amino-5-hydroxy-5-phosphonovaleric acid (1).
Hydrolysis of 4–5 mmol of phosphonate 2 or 4 in 10–
4 mL of a mixture of concentrated hydrochloric and
1
acetic acids (1 : 1) was carried out for 13–15 h. The
reaction mixture was evaporated in a vacuum, the
residue was co-evaporated with water and chromato-
graphed on the cation exchanger eluting with 1 N HCl.
Positive ninhydrin fractions were combined and
evaporated in a vacuum, the residue was treated in an
aqueous alcohol with excess of propylene oxide and
1
.
Kukhar, V.P. and Hudson, H.R., Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
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75, 127.
2
3
. Wolf, M.S., J. Med. Chem., 2012, vol. 55, no. 21,
p. 8977. doi 10.1021/jm301426y
crystallized from the alcohol. Yield 63–71%, mp 221–
. Claesson, A., Swahn, B.-M., Edvinsson, K.M., Molin, H.,
and Sandberg, M., Bioorg. Med. Chem. Lett., 1992, vol. 2,
p. 1247. doi 10.1016/S0960-894X(00)80223-1
1
2
1
(
23°C (decomp.). H NMR spectrum (D О), δ, ppm:
2
.50–2.25 m (4Н, СН ), 3.65 br. t (1Н, СHN), 3.97 m
1Н, СHО). С NMR spectrum (D О), δ , ppm: 26.22
d ( J = 4.6 Hz), 26.40 d ( J = 6.1 Hz), 52.35 d (CN,
JРC = 4.6 Hz), 66.34 d (CHOH, J = 161.8 Hz),
71.38 (C=O). Р NMR spectrum (D О): δ 24.1 ppm.
Mass spectrum (LCМS), m/z: 214.1 [M + H] (cal-
culated for C H NO P: 213.1). Found, %: C 27.92,
2
1
3
2 С
4
5
. Bigge, С.F., Wu, J.-P., Malone, T.C., Taylor, C.P., and
Vartaian, M.G., Bioorg. Med. Chem. Lett., 1993, vol. 3,
p. 39. doi 10.1016/S0960-894X(00)80088-8
2
3
РC
РC
4
1
РC
3
1
1
2 Р
. Lemonnier, G., Lion, C., Quirion, J.-C., Pin, J.-P., Goudet, C.,
and Jubault, P., Bioorg. Med. Chem., 2012, vol. 20,
p. 4716. doi 10.1016/j.bmc.2012.06.006
+
5
12
6
2
8.07; H 5.84, 5.90; N 6.33, 6.22; P 14.31, 14.23.
6
7
. Gancarz, R. and Gancarz, I., Tetrahedron Lett., 1993,
vol. 34, p. 145. doi 10.1016/S0040-4039(00)60079-5
C H NO P. Calculated, %: C 28.18; H 5.68; N 6.57; P
5
12
6
1
4.53.
. Moe, O.A. and Warner, D.T., J. Am. Chem. Soc., 1948,
1
31
13
13
vol. 70, no. 8, p. 2763. doi 10.1021/ja01188a037
H, P, C, C Dept NMR spectra were recorded
on a Bruker DPX-200 spectrometer. Melting points
were determined on a heating block in an open
capillaries. For column chromatography silica gel
L60/200 (Alfa Aesar) was used, chromatographic
analysis was carried out on an Agilent 1100 LC/MSD
8. Golebiewski, W.M., Bull. Polish Acad. Sci. Chem.,
1989, vol. 36, nos. 9–12, p. 425.
9. Gardini, G.P. and Palla, G., J. Label. Compd.
Radiopharm., 1977, vol. 13, no. 3, p. 339. doi 10.1002/
jlcr.2580130307
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 9 2018