Addition of morpholine and pyrrolidine to isopropenylphosphonic acid in situ

Full text of DOI:10.1134/S1070428013040258

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 4, pp. 627–628. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.E. Bal’tser, D.A. Zaitsev, T.V. Ivanova, T.G. Babenko, E.N. Barskova, 2013, published in Zhurnal Organicheskoi Khimii, 2013,
Vol. 49, No. 4, pp. 642–643.
SHORT
COMMUNICATIONS
Dedicated to the 100th Anniversary of Corresponding Member
of the Russian Academy of Sciences A.A. Petrov
Addition of Morpholine and Pyrrolidine
to Isopropenylphosphonic Acid in situ
A. E. Bal’tser, D. A. Zaitsev, T. V. Ivanova, T. G. Babenko, and E. N. Barskova
“
Applied Chemistry” Russian Scientific Center, ul. Krylenko 26A, St. Petersburg, 193232 Russia
e-mail: fominarscac@mail.ru
Received January 28, 2013
DOI: 10.1134/S1070428013040258
Aminoalkylphosphonic acids exhibit a high anticor-
rosion effect toward carbon and low-alloy steels [1–2].
A large number of compounds of this type were syn-
thesized by aminoalkylation of phosphonic acid deriv-
atives [3].
this way contain a one-carbon bridge connecting the
nitrogen and phosphorus atoms, whereas extension of
that bridge should lead to increased size of the dipole
and enhanced adsorbance, which should improve pro-
tective properties of corrosion inhibitor. This problem
was successfully solved in the present work. We pro-
pose a new synthesis of aminoalkylphosphonic acids
containing two carbon atoms between the nitrogen and
phosphorus atoms. The procedure is based on the reac-
tion of secondary amines with ispropenylphosphonic
N(CH CH NH ) [C(X)(Y)P(O)(OH) ]
2 p
2
2
n m
n = 0, 1; m = 0–3; p = 1, 2.
We previously studied Mannich aminoalkylation of
phosphonic acid with cyclic amines, pyrrolidine and
morpholine, with the use of formaldehyde, acetone,
and ethyl methyl ketone as carbonyl component [4]
acid (I) generated in situ from acetone and PCl in
3
the presence of acetic acid [7] (Scheme 2).
Scheme 2.
(
Scheme 1).
Me
O
O
2
AcOH
+
PCl3
Scheme 1.
H C
2
P
OH
–
2AcCl, –HCl
Me
Me
O
OH
NH
+
+
P(OH)3
(
)n
I
R1
R2
X
R1
R2
O
P
Unsaturated phosphonic acid I was brought into
the copolymerization with acrylates immediately after
removal of volatile components without additional
purification [7].
+
H , 80–130°C
N
OH
(
)n
OH
X
1
2
R = R = H, Me, Et; X = O, n = 2; X = CH
2
, n = 1.
We have reproduced the synthesis of I and con-
firmed its structure by NMR spectroscopy in D O.
2
1
According to the H NMR data, like all known
1
The H NMR spectrum of I contained a doublet at
aminoalkylphosphonic acids [5, 6], the products in
solution had zwitterionic structure which ensured their
high adsorption ability and strong protective effect on
metal surface.
δ 1.55/1.58 ppm due to methyl protons (3H) and
a quartet at δ 5.32–5.47 ppm from the CH = group
2
13
(
2H). In the C NMR spectrum of I, the CH group
3
gave a doublet at δ 17.61/17.74 ppm, and doublets at
C
However, due to specific features of the Mannich
reaction, all aminoalkylphosphonic acids obtained in
δ 128.07/128.17 (CH =) and 134.91/136.60 ppm
C
2
(=CP) were present. Compound I displayed only one
6
27

6
28
BAL’TSER et al.
3
1
1
signal at δ –18.34 ppm in the P NMR spectrum. The
1105. H NMR spectrum, δ, ppm: 1.28 m (3H, CH ),
P
3
product also contained traces of an inorganic phos-
phorus impurity. The presence of double C=C bond in
molecule I was confirmed by titration with bromine
1.55 m (1H, CH), 1.99 m (2H, CH ); 3.44 m, 3.58 m,
2
and 3.62 m (8H, C H NO). Found, %: C 40.05;
4
8
H 7.39; N 6.29; P 14.75. C H NO P. Calculated, %:
7
16
4
(
the bromine number was close to the theoretical
C 40.19; H 7.66; N 6.70; P 14.83.
value).
1
-(Pyrrolidin-1-yl)propan-2-ylphosphonic acid
The reactions of morpholine (II) and pyrrolidine
III) with isopropenylphosphonic acid (I) produced
(V) was synthesized in a similar way from 88 ml
(1.05 mol) of pyrrolidine. The reaction mixture was
stirred for 10 h at 80–85°C. Yield 194 g (96%). IR
(
1
-(morpholin-4-yl)propan-2-yl- and 1-(pyrrolidin-1-
–
1
yl)propan-2-ylphosphonic acids IV and V, respectively
spectrum, ν, cm : 3375 br, 2980 br (OH), 2765, 1638,
1
(
Scheme 3). Compounds IV and V were isolated as
1180 (P=O, P–O), 1463, 1390 (CH). H NMR spec-
brown transparent viscous homogeneous liquids,
which are readily soluble in water and almost insoluble
in organic solvents. Their structure was confirmed by
trum, δ, ppm: 1.51 m and 1.55 m (3H, CH ); 1.81 m,
3
1.94 m, and 3.46 m (8N, C H N); 3.60 m (2H, CH ),
4
8
2
3.63 m (1H, CH) Found, %: C 43.11; H 8.21; N 7.01;
P 15.89. C H NO P. Calculated, %: C 43.52; H 8.29;
1
elemental analyses and IR and H NMR spectra.
7
16
3
N 7.25; P 16.06.
Scheme 3.
The IR spectra were recorded from thin films on
OH
1
13
Me
a Shimadzu FTIR 8400 spectrometer. The H, C, and
O
P
OH
31
NH
)n
P NMR spectra were obtained on a Bruker Avance III
N
+
H C
P
OH
O
2
(
400 instrument from solutions in D O.
2
X
( )
n
Me
IV, V
OH
X
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (state contract no. 16.523.12.3008,
September 13, 2011).
I
II, III
II, IV, X = O, n = 2; III, V, X = CH , n = 1.
2
Thus we have developed a convenient procedure
for the synthesis of 1-aminopropan-2-ylphosphonic
acids from acetone, phosphorus trichloride, and cyclic
secondary amine; we plan to extend the developed
procedure to other amines.
-(Morpholin-4-yl)propan-2-ylphosphonic acid
IV). Phosphorus trichloride, 93 ml (1.05 mol), was
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2
1
(
added under stirring to 77 ml (1.05 mol) of acetone,
the mixture was stirred for 4.5 h, and 300 ml of acetic
acid was gradually added over a period of 2 h; the
addition of acetic acid was accompanied by vigorous
evolution of hydrogen chloride. The mixture was
stirred for 12 h at 50–60°C, volatile components were
distilled off first under atmospheric pressure and then
under reduced pressure (2 mm), maintaining the tem-
perature at 160°C. Morpholine, 91 ml (1.05 mol), was
added in portions to the residue under stirring, and the
mixture was stirred for 10 h at 60–80°C. Yield 208 g
3
4
5
. Derek, R., US Patent no. 3743603, 1973; Ref. Zh., Khim.,
1
974, no. 9N81P.
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6
–
1
(
95%). IR spectrum, ν, cm : 3380 br, 2970 br (OH),
765, 1632, 1180 (P=O, P–O), 1461, 1385 (CH), 2460,
7. Becker, L.W., US Patent no. 4446028, 1984; Ref. Zh.,
2
Khim., 1985, no. 5T418P.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 4 2013