Intramolecular cyclization of 1,3-diamino-2-hydroxypropan-N,N,ń,ń-tetrakis(methylphosphonic acid) upon phosphonomethylation of 1,3-diaminopropan-2-ol

Article abstract of DOI:10.1007/s11172-015-1001-8

Phosphonomethylation of 1,3-diaminopropan-2-ol affords the mixture of 1,3-diamino-2-hydroxypropan-N,N,ń,ń-tetrakis(methylphosphonic acid) (1) with its cyclic ether, viz., [(6-[bis(phosphonomethyl)amino]methyl-2-hydroxy-2-oxido-1,4,2-oxazaphosphinan-4-yl)methyl]phosphonic acid (2), but not 1, as assumed earlier.

Full text of DOI:10.1007/s11172-015-1001-8

1
200
Russian Chemical Bulletin, International Edition, Vol. 64, No. 5, pp. 1200—1201, May, 2015
Intramolecular cyclization of 1,3ꢀdiaminoꢀ2ꢀhydroxypropanꢀ
N,N,N´,N´ꢀtetrakis(methylphosphonic acid) upon phosphonomethylation
of 1,3ꢀdiaminopropanꢀ2ꢀol
N. V. Tsirul´nikova, Ya. V. Bolt, and S. K. Belus
State Scientific Research Institute of Chemical Reagents and High Purity Chemical Substances,
3
ul. Bogorodsky val, 107076 Moscow, Russian Federation.
Tel. +7 (495) 963 7457. Eꢀmail: nv.tsir@mail.ru
Phosphonomethylation of 1,3ꢀdiaminopropanꢀ2ꢀol affords the mixture of 1,3ꢀdiaminoꢀ2ꢀ
hydroxypropanꢀN,N,N´,N´ꢀtetrakis(methylphosphonic acid) (1) with its cyclic ether, viz.,
[(6ꢀ{[bis(phosphonomethyl)amino]methyl}ꢀ2ꢀhydroxyꢀ2ꢀoxidoꢀ1,4,2ꢀoxazaphosphinanꢀ4ꢀyl)ꢀ
methyl]phosphonic acid (2), but not 1, as assumed earlier.
Key words: 1,3ꢀdiaminopropanꢀ2ꢀol, phosphonomethylation, NMR spectroscopy, 1,3ꢀdiꢀ
aminoꢀ2ꢀhydroxypropanꢀN,N,N´,N´ꢀtetrakis(methylphosphonic acid), cyclic ester.
The chelating agent synthesized for the first time by
ing phosphonomethylation of 2ꢀaminoethanol,5—7 from
which 2ꢀhydroxyethylaminoꢀN,Nꢀbis(methylphosphonic
acid) (3) and its intramolecular ester, [(2ꢀhydroxyꢀ2ꢀoxidoꢀ
1,4,2ꢀoxazaphosphinanꢀ4ꢀyl)methyl]phosphonic acid (4),
were isolated (Scheme 2).
Soviet scientists in the beginning of 1980s, viz., methylꢀ
phosphorylated 1,3ꢀdiaminopropanꢀ2ꢀol derivative,1 was
found to be an efficient inhibitor of mineral salt deposition
for water stabilization treatment in water utilization sysꢀ
tems, which is superior to the sameꢀpurpose reagents in
,2
To determine the composition of the mixture under
study, we performed the comparative analysis of the
3
,4
consumer properties. The authors of Ref. 2 characterꢀ
ized the obtained product as 1,3ꢀdiaminoꢀ2ꢀhydroxyꢀ
propanꢀN,N,N´,N´ꢀtetrakis(methylphosphonic acid) (1)
based on the data from IR spectroscopy.
13
1
31
1
C{ H} and P{ H} NMR spectra of this mixture and
model compounds 3 and 4, which confirmed the assumpꢀ
tion of that, along with acid 1, the phosphonomethylation
product of 1,3ꢀdiaminopropanꢀ2ꢀol contains its intramoꢀ
Based on the 1 C{ H} and P NMR{ H} spectral study
of phosphonomethylated 1,3ꢀdiaminopropanꢀ2ꢀol derivꢀ
ative obtained by the Kabachnik—Fields reaction, we
found for the first time that the product is a mixture of
phosphorusꢀcontaining 1,3ꢀdiaminopropanꢀ2ꢀol derivaꢀ
tives, which are difficult to separate.
3
1
31
1
13
1
lecular cyclic ester 2: the C{ H} NMR spectra of the
mixture display identicalꢀintensity signals for two methylꢀ
ene and one methyne group of the 1,4,2ꢀoxazaphosphiꢀ
nane heterocycle whose fine structures correspond to the
positions and multiplicities of the signals for the ring carꢀ
13
1
We have assumed that the resulted mixture along with
acid 1 contains its intramolecular cyclic ester, viz., [(6ꢀ{[bisꢀ
phosphonomethyl)amino]methyl}ꢀ2ꢀhydroxyꢀ2ꢀoxidoꢀ
,4,2ꢀoxazaphosphinanꢀ4ꢀyl)methyl]phosphonic acid (2)
Scheme 1) by the analogy with the mixture formed durꢀ
bon atoms observed in the C{ H} NMR spectra of the
model compound 4 (Table 1) which proves the presence of
compound 2 in the mixture under study
(
1
(
The contents of acids 1 and 2 in the mixture according to
the 31P{ H} spectral data were 56% and 44%, respectively.
1
Scheme 1
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1200—1201, May, 2015.
066ꢀ5285/15/6404ꢀ1200 © 2015 Springer Science+Business Media, Inc.
1

Methylphosphorylation of 1,3ꢀdiaminopropanꢀ2ꢀol
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 5, May, 2015
1201
Table 1. 13C{ H} NMR spectra (D O) of the mixture of compounds 1 and 2 and model compounds 3 and 4
1
2
Atom
 (J/Hz)
1
2
3
4
С(3)
52.47 (dd, J = 135.9,
50.18 (dd, J = 131.5,
51.52 (dd, J = 136.7,
51.05 (dd, J = 128.4,
C,P
C,P
C,P
C,P
3
3
3
3
JC,P = 3.3)
JC,P = 3.9)
JC,P = 4.1)
JC,P = 4.4)
3
3
3
3
С(5)
С(6)
С(7)
58.59 (t, J = 2.7)
54.84 (t, J = 3.3)
57.82 (t, J
= 3.1)
54.25 (t, J
= 5.0)
C,P
C,P
C,P
C,P
2
2
60.71 (s)
67.32 (d, J = 4.5)
55.13 (s)
61.83 (d, J = 5.0)
C,P
C,P
55.13 (dd, JC,P = 135.9,
54.73 (dd, JC,P = 136.5,
3
3
JC,P = 8.3)
JC,P = 7.7)
3
С(9)
56.02 (t, J = 2.8)
C,P
С(11)
52.14 (dd, JC,P = 135.9,
JC,P = 4.4)
3
Scheme 2
2ꢀHydroxyethylaminoꢀN,Nꢀbis(methylphosphonic acid) (3)
was prepared under the conditions of the earlier described synꢀ
6
thesis as tetrasodium salt, which was transformed into the acid
by acidification of a cooled to 0 C solution of the salt with 36%
HCl until pH 1.5. The precipitate that formed was filtered off, the
filtrate was evaporated to 1/3 of the starting volume, and the
residue was added dropwise with stirring to DMF (150 mL). The
crystalline precipitated product was filtered off, washed with
DMF (2×20 mL), and dried in vacuo to yield acid 2 (76.0 g, 71%),
m.p. 264—266 C (decomp.). 3 P{ H} NMR (D O), : 8.4 (s).
1
1
2
This work was financially supported by the Ministry of
Education and Science of the Russian Federation (Aid Grant
Agreement No. 14.576.21.0017 dated on June 23, 2014).
References
1
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8
76666; Bull. Izobret., 1981, 40 (in Russian).
1
3
1
31
1
C{ H} and P{ H} NMR spectra were recorded on a Bruker
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tivy i osobo chistye veshestva. Primenenie kompleksonov v nefteꢀ
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stances. Application of Chelating Agents in OilꢀProducing Indusꢀ
try], NIITEKhIM, Moscow, 1983, 48 pp. (in Russian)
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AVANCE III NanoBay (75.51 and 121.56 MHz, respectively)
instrument in D O in standard tubes with an external diameter
of 5 mm at 25 C. Melting points were determined on a Stuart
SMP30 Melting Point Apparatus.
Phosphonomethylation of 1,3ꢀdiaminopropanꢀ2ꢀol. To 36%
HCl (28.2 mL, 0.33 mol), 1,3ꢀdiaminopropanꢀ2ꢀol (13.5 g,
.15 mol) was added portionwise at 0 C and, then, 61.8% aqueous
solution of H PO (57.6 mL, 0.60 mol) was added. 37% formalin
18.9 mL, 0.63 mol) was added dropwise to the resulted mixture
2
0
3
3
(
at 106 C and the solution was heated for 3 h at 106 C and
evaporated to 1/3 of the starting volume. The residue was added
dropwise to methanol taken in the sevenꢀfold volume. The crysꢀ
talline precipitated product was filtered off, washed with methaꢀ
nol (2×50 mL), and dried in vacuo to yield a hygroscopic product
1
1
(
(
45.4 g). 3 P{ H} NMR (D O), : 4.0 (s, 1 P, P(2) (2)); 6.2
s, 1 P, P(8) (2)); 7.0 (s, 2 P, P(12) (2)); 7.2 (s, 4 P (1)).
2
[
(2ꢀHydroxyꢀ2ꢀoxidoꢀ1,4,2ꢀoxazaphosphinanꢀ4ꢀyl)methyl]ꢀ
phosphonic acid (4) was prepared by the procedure described in
Ref. 6. M.p. 258—261 C (decomp.) (data of Ref. 6: 258—260 C
decomp.)). 3 P{ H} NMR (D O), : 4.8 (s, 1 P, P(2)); 7.6
1
1
Received October 27, 2014;
(
2
(
s, 1 P, P(8)).
in revised form February 5, 2015