Green synthesis of poly(aminomethylenephosphonic) acids

Article abstract of DOI:10.1080/10426501003724897

The reaction of polyamines with phosphorous acid and formaldehyde in water under focused microwave irradiation provides a facile and rapid synthesis of poly(aminomethylenephosphonic) acids. Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
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Green Synthesis of
Poly(aminomethylenephosphonic) Acids
Didier Villemin a , Bernard Moreau a , Abdelghani Elbilali a ,
Mohamed-Amine Didi b , M’hamed Kaid b & Paul-Alain Jaffrès a
a Laboratoire de Chimie Moléculaire et Thioorganique, UMR CNRS
6507, INC3M, FR 3038, ENSICAEN & Université de Caen, Caen,
France
b Laboratoire des Technologies de Séparation et Purification,
Département de chimie, Faculté des Sciences, Université de
Tlemcen, Algérie
Published online: 19 Nov 2010.
To cite this article: Didier Villemin , Bernard Moreau , Abdelghani Elbilali , Mohamed-Amine Didi ,
M’hamed Kaid & Paul-Alain Jaffrès (2010): Green Synthesis of Poly(aminomethylenephosphonic) Acids,
Phosphorus, Sulfur, and Silicon and the Related Elements, 185:12, 2511-2519
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Phosphorus, Sulfur, and Silicon, 185:2511–2519, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003724897
GREEN SYNTHESIS OF
POLY(AMINOMETHYLENEPHOSPHONIC) ACIDS
Didier Villemin,1 Bernard Moreau,1 Abdelghani Elbilali,1
Mohamed-Amine Didi,2 M’hamed Kaid,2
and Paul-Alain Jaffre`s1
1Laboratoire de Chimie Mole´culaire et Thioorganique, UMR CNRS 6507, INC3M,
FR 3038, ENSICAEN & Universite´ de Caen, Caen, France
2Laboratoire des Technologies de Se´paration et Purification, De´partement de
chimie, Faculte´ des Sciences, Universite´ de Tlemcen, Alge´rie
The reaction of polyamines with phosphorous acid and formaldehyde in wa-
ter under focused microwave irradiation provides a facile and rapid synthesis of
poly(aminomethylenephosphonic) acids.
Keywords Metal extractant; microwave irradiation; polyphosphonic acid; water solvent
INTRODUCTION
Aminophosphonic acids constitute an important class of biologically active com-
pounds, and their synthesis has been a focus of considerable attention in synthetic organic
chemistry as well as in medicinal chemistry.1 These acids are considered to be structural
analogues of the corresponding amino acids. Thus, acting as competitive inhibitors, they
can act as false substrates during the course of amino acid metabolism. Aminophosphonic
acids are also very good ligands for the coordination of metal ions so they can be used for the
extraction of metals such as iron, copper, nickel, and uranium in hydrometallurgy.2 These
acids also form complexes on the surface of metals such as iron3 and consequently are very
suitable as anticorrosion agents.4 These acids are also precursors of organic materials5 or
hybrid materials for metal organic frameworks (MOF).6 The phosphonic acids can be also
Received 9 December 2009; accepted 23 February 2010.
We gratefully acknowledge the PunchOrga Network (Poˆle Universitaire Normand de Chimie Organique), the
Ministe`re de la Recherche et des Nouvelles Technologies, CNRS (Centre National de la Recherche Scientifique),
the Re´gion Basse-Normandie, the European Union (FEDER funding), and CMEP-TASSILI No 10MDU799 for
their financial support, and the BASF for their generous gift of polyethylenimines (LupasolꢀR ).
The present affiliation for is Paul-Alain Jaffre`s CEMCA, UMR CNRS 6521, Universite´ de Bretagne Occi-
dentale, Brest, France.
Address correspondence to Didier Villemin, Laboratoire de Chimie Mole´culaire et Thioorganique,
UMR CNRS 6507, INC3M, FR 3038, ENSICAEN & Universite´ de Caen, 14050 Caen, France. E-mail:
didier.villemin@ensicaen.fr
2511

2512
D. VILLEMIN ET AL.
useful for the modification of inorganic surfaces or for grafting organic compounds on in-
organic surfaces.7 They can be used for making supported catalysts8 or modified inorganic
nanoparticles,9 and they can also be used as enzyme inhibitors.10
RESULTS AND DISCUSSION
The aminophosphonic acids are generally obtained by hydrolysis of esters obtained
via the Kabachnik–Fields reaction11 of a carbonyl compound, a dialkylphosphite, and
an amine. The Kabachnik–Fields reaction can be efficiently activated by microwave ir-
radiation;12 nevertheless there are often secondary reactions during the subsequent hy-
drolysis of the phosphonate. The Irani–Moedritzer13 synthesis is less general than the
Kabachnik–Fields reaction, but it has the advantage of giving the aminophosphonic acid
directly without a hydrolysis step. The Irani–Moedritzer reaction times are in general long,
so the use of microwave irradiation for assisting the reaction is of interest. We describe
this reaction in aqueous medium without organic solvent under focused microwave irradia-
tion. Water is an inexpensive, nonflammable, nontoxic solvent, and it has the advantage of
warming up quickly under microwave irradiation. Carrying out reactions using microwave
heating, as opposed to conventional heating, has the major advantage of shorter reaction
times because of the rapid heating.14
The Irani–Moedritzer reaction can be compared with a Mannich reaction and takes
place by the addition of phosphorous acid to the iminium salt formed by reaction of an
aqueous solution of formaldehyde with the amine in acidic medium.
We obtained various polyaminopolymethylenephosphonic acids by refluxing
polyaminoalkanes with phosphorous acid and formaldehyde in hydrochloric media
(Schemes 1 and 2) under microwave irradiation in a resonance mono-mode cavity.
microwave
H2N (CH2)n NH2 + 4 H3PO3
n= 1 to 10
( (HO)2POCH2)2N
(CH2)n N(CH2PO (OH)2)2
+ 4 HCHO
HCl, H2O
Scheme 1 Synthesis of diaminoalkane-N,N,N’,N’-tetrakis(methanephosphonic acids) from diaminoalkanes.
Although the reaction also takes place under multimode irradiation by the use of a
commercial furnace, the yields obtained are worse. After cooling and evaporation of half
the volume of water, the aminophosphosphonic acid crystallized as a white solid. It was
then recrystallized in a water–isopropanol mixture.
(HO)2OP
H2N
PO(OH)2
PO(OH)2
NH2
microwave
N
N
(HO)2OP
+
4 H3PO
3 + 4 HCHO
HCl, H2O
Scheme 2 Synthesis of diaminoalkane-N,N,N’,N’-tetrakis(methanephosphonic acids) from diaminoalkanes.
The yields reported in the literature correspond to the crude products, and it is
necessary to recrystallize the acids in order to obtain pure products according to their
31P NMR spectra. That can pose problems when the acids are very soluble in water, e.g.,
compound 2 is obtained as a crude product with 95% yield, but after recrystallization, only
63% of pure product is obtained due to its high solubility in water.

SYNTHESIS OF POLY(AMINOMETHYLENEPHOSPHONIC) ACIDS
2513
With the dendritic polyethylenimine of different molecular mass range (Mw = 20000
to 750000), we have obtained polymeric aminophosphonic acids useful as resins for ex-
traction of metal ions and anticorrosion agent (Scheme 3).
CH2 PO(OH)2
H3PO3,HCl, H2O, HCHO
-(CH2-CH2-NH)n-
-(CH2-CH2-N-)n-
microwave
Scheme 3 Synthesis of diaminoalkane-N,N,N’,N’-tetrakis(methanephosphonic acids) from diaminoalkanes.
The reactions were carried out in a tubular reactor fitted with an effective cooling
mechanism, which permits refluxing of the solution without the formaldehyde escaping
from the reaction media. This reactor was irradiated in a resonance mono-mode cavity.
Although the reactions also took place under multimode irradiation of a commercial furnace,
the yields obtained were worse.
After cooling and evaporation of half the volume of water, the aminomethanephospho-
sphonic acid crystallized as a white solid. It was then recrystallized in a water–isopropanol
mixture. The activation by microwaves allows better yields than conventional heating.
Many of these polyphosphonic acids were prepared previously under classical re-
flux conditions,15 but since their spectra were generally not reported in the literature, we
systematically describe their NMR spectroscopic properties here.
CONCLUSION
The one-pot synthesis of polyaminophosphonic acids under microwave irradiation is
general, simple, fast, and efficient, and it allows interesting aminophosphonic acids to be
obtained which are useful as biologically active molecules, coordinating agents of metals,
or precursors of materials (organic or MOF).
EXPERIMENTAL
Instrumentation
The infrared spectra were recorded on a Perkin-Elmer Spectrum One spectrometer
equipped with accessories ATR. Samples were analyzed NMR spectroscopically by use of a
multinuclear Bruker B 400 FT-spectrometer. Samples of the products were diluted in D2O in
the presence of Na2CO3. Microwave irradiation reactions were performed in a mono-mode
resonance microwave oven (Synthewave 402, Prolabo) working with the frequency of 2450
MHz, controlled with an IR thermometer and monitoring by a computer. Microanalyses
ꢀR
were performed on the automatic C,H,N analyzer Thermoquest. The membrane Nadir
was utilized for the dialyses.
Chemicals
All chemicals used except for polyethylenimines were from Aldrich or Fluka.
ꢀR
Polyethylenimines (Lupasol ) were gifted by BASF.

2514
D. VILLEMIN ET AL.
Diaminomethane-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (1)
A mixture of diaminomethane dihydrochloride (2.38 g, 20 mmol), phosphorous acid
(6.56 g, 80 mmol), water (5mL), hydrochloric acid (36%, 4 mL), and formaldehyde (37%,
7.5 mL, 100 mmol) was irradiated in a glass cylinder reactor fitted with a cooler filled
under microwave irradiation at 240 W for 10 min. After cooling and evaporation, a white
solid was obtained after filtration. The product (1) is very soluble in water, and only a
small part was crystallized (yield: 15%) although the phosphonation was quantitative (31P
NMR). 1H NMR: 2.96–2.99 (m, 2H, N-CH2), 3.66 (d, 2JHP = 12.50 Hz, 8H, N-CH2-P);
13C NMR: 44.61 (CH2-N), 52.89 (d, 1JCP = 137.70 Hz, N-CH2-P); 54.61 1JCP = 135.20
Hz, N-CH2-P); 31P NMR: 7.89.
1,2-Diaminoethane-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (2)
A mixture of 1,2-diaminoethane (0.6 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was microwave irradiated
240 W for 2 min. After this, formaldehyde (6 mL, 80 mmol) was added rapidly, and the
mixture was irradiated for 10 min at 240 W. After cooling and evaporation, a white solid
was obtained after filtration. Yield 63%; mp: 247◦C; 1H NMR: 2.94 (d, 2JHP = 11.20 Hz,
1
8H, N-CH2-P), 3.35–3.39 (m, 4H, N-CH2); 13C NMR: 52.28 (CH2-N), 53.0 (d, JCP
=
135.20 Hz, N-CH2-P); 31P NMR: 7.41; IR (cm−1): 2286 (νP-OH), 1105 (νP = O), 1010, and
944(νP-O).
1,3-Diaminopropane-N,N,N’,N’-tetrakis(methanenephosphonic Acid)
(3)
A mixture of 1,3-diaminopropane (0.85 mL, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was microwave irradiated at
240 W for 2 min. After this, formaldehyde (6 mL, 80 mmol) was added rapidly, and the
mixture was irradiated for 12 min at 240 W. After cooling and evaporation, the precipitate
was filtered, and the white solid was washed with acetone and water. Yield 64%; mp:
130◦C; 1H NMR: 1.93–1.97 (m, 2H), 3.21 (d, 2JHP = 11.30 Hz, 8H, N-CH2-P), 3.33–3.37
(m, 4H); 13C NMR: 19.11, 42.0, 50.91 (d, 1JCP = 138.0 Hz, N-CH2-P); 31P NMR: 8.45; IR
(cm−1): 3000 (νOH), 1471 (νP = O), 917(νP-O).
1,4-Diaminobutane-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (4)
A mixture of 1,4-diaminobutane (0.88 g, 10 mmol.), phosphorous acid (3.28 g,
40 mmol), water (3 mL), hydrochloric acid (36%, 3 mL), and formaldehyde (6 mL, 80 mmol)
was irradiated at 240 W for 15 min. After cooling and evaporation, the precipitate was
filtered, and the white solid was washed with a mixture of 2-propanol and water. Yield
68%; mp: 240◦C; 1H NMR: 1.74–1.78 (m, 4H), 3.16 (d, 2JHP = 11.40 Hz, 8H, N-CH2-P),
1
3.43–3.48 (m, 4H); 13C NMR: 20.41, 51.89 (d, JCP = 136.0 Hz, N-CH2-P), 55.80; 31P
NMR: 6.51.
1,6-Diaminohexane-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (5)
A mixture of 1,6-diaminohexane (1.16 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated at 240 W for
2 min. After this, formaldehyde (6 mL, 80 mmol) was added rapidly, and the mixture was

SYNTHESIS OF POLY(AMINOMETHYLENEPHOSPHONIC) ACIDS
2515
irradiated for 20 min at 240 W. After cooling and evaporation, the precipitated was filtered
and the white solid was washed with water. Yield 91%; mp: 242◦C; 1H NMR: 1.26–1.30
(m, 4H), 1.63–1.67 (m, 4H), 3.32–3.36 (m, 4H), 3.65 (d, 2JHP = 13.20 Hz, 8H, N-CH2-P);
13C NMR: 21.11; 23.20; 34.89; 49.52 (d, 1JCP = 136.70 Hz, CH2-P). 31P NMR: 7.79; IR
(cm−1): 2750 (νOH), 2362 (νP-OH), 1178 (νP = O), 1020 and 944 (νP-O).
1,7-Diaminoheptane-N,N,N’,N’-tetrakis(methanenephosphonic Acid)
(6)
A mixture of 1,7-diaminohexane (2.6 g, 20 mmol), phosphorous acid (6.56 g,
80 mmol), water (15 mL), and hydrochloric acid (36%, 6 mL) was irradiated in a glass
cylinder reactor fitted by a cooler filled at 240 W for 2 min. After this, formaldehyde
(12 mL, 160 mmol) was added rapidly, and the mixture was irradiated for 15 min at 240
W. After cooling, water and acetone were added. Two immiscible phases were obtained;
the upper phase was the product. After evaporation of solvent, 6 was obtained as a white
1
solid. Yield 62%; H NMR: 1.23–1.27 (m, 6H), 1.61–1.65 (m, 4H), 3.35 (t, J = 8.0 Hz,
4H), 3.43 (d, 2JHP = 12.80 Hz, 8H, N-CH2-P); 13C NMR: 22.50; 24.69; 27.11; 50.62 (d,
1JCP = 138.20 Hz, CH2-P); 56.71; 31P NMR: 8.10; IR(cm−1): 2758 (νOH), 2165 (νPOH),
1135 (νP = O), 1002 and 928 (νPO).
1,8-Diaminooctan-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (7)
A mixture of 1,8-diaminooctane (1.44 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (4 mL), hydrochloric acid (36%, 4 mL), and formaldehyde (6 mL,
80 mmol) was irradiated for 15 min at 240 W. After cooling and evaporation, the pre-
cipitate was filtered, and the white solid was washed with acetone and water. Yield 64%;
1
2
mp: 248◦C; H NMR: 1.24–1.28 (m, 8H), 1.62–1.66 (m, 4H), 3.14 (d, JHP = 11.40 Hz,
8H, N-CH2-P), 3.37 (t, J = 7.40 Hz, 4H). 13C NMR: 23.30, 25.55, 28.21, 52.0, 53.29 (d,
1JCP = 136.20 Hz, CH2-P); 31P NMR: 6.71.
1,9-Diaminononane-N,N,N’,N’-tetrakis(methanenephosphonic Acid) (8)
A mixture of 1,9-diaminononane (1.58 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), hydrochloric acid (36%, 4 mL), and formaldehyde (6 mL, 80 mmol)
was irradiated for 15 min at 240 W. After cooling and evaporation, the precipitate was
crystallized in water, 2-propanol, and acetone. Yield (80%); 1H NMR: 1.24–1.28 (m, 10H),
1.66–1.69 (m, 4H), 3.46 (d, 2JHP = 12.80 Hz, 8H, N-CH2-P), 3.41 (t, J = 8.0 Hz, 4H); 13
C
1
NMR: 23.01, 25.30, 27.78, 27.91, 51.14 (d, JCP = 132.90 Hz, CH2-P), 57.0; 31P NMR:
7.71.
1,10-Diaminodecane-N,N,N’,N’-tetrakis(methanenephosphonic Acid)
(9)
A mixture of 1,10-diaminodecane (1.72 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), hydrochloric acid (36%, 4 mL), and formaldehyde (6 mL, 80 mmol)
was irradiated for 15 min at 240 W. After cooling and evaporation, the precipitate was
1
filtered, and the white solid was washed with acetone and water. Yield 80%; H NMR:
2
1.24–1.28 (m, 12H), 1.66–1.69 (m, 4H), 3.17 (d, JHP = 11.20 Hz, 8H, N-CH2-P), 3.41

2516
D. VILLEMIN ET AL.
1
(t, J = 8.0 Hz, 4H); 13C NMR: 23.40, 25.75, 28.51, 28.59, 53.86 (d, JCP = 125.50 Hz,
CH2-P), 56.80; 31P NMR: 6.59.
1,12-Diaminododecane-N,N,N’,N’-tetrakis(methanenephosphonic acid)
(10)
A mixture of 1,12-diaminododecane (2 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated at 240 W for
2 min. After this, formaldehyde (3.3 mL, 44 mmol) was added rapidly, and the mixture
was irradiated for 30 min at 240 W. After cooling and evaporation, the precipitated was
filtered, and the white solid was washed with acetone and water. Yield 93%; mp: 230◦C; 1H
NMR: 1.13–1.18 (m, 16H), 1.56–1.61 (m, 4H), 3.10 (d, 2JHP = 11.20 Hz, 8H, N-CH2-P),
3.32 (t, J = 7.70 Hz, 4H); 13C NMR: 22.79, 25.11, 27.79, 28.02, 28.12, 52.81 (d, 1JCP
=
126.50 Hz, CH2-P); 31P NMR: 7.83; IR (cm−1): 2919 (νOH), 2275 (νP = O), 1151 (νP = O),
936 (νP-O), 585 (νCH).
Piperazine-N,N’-bis(methanephosphonic Acid) (11)
Piperazine (0.86 g, 10 mmol) in a quartz tube with a cooler was added to a mixture
of phosphorous acid (1.64 g, 20 mmol), water (3 mL), and hydrochloric acid (3 mL). Then
formaldehyde (3 mL, 40 mmol) was added, and the unit was irradiated at 240 W for 15
min. The product precipitated directly in the tube; it was filtered and washed with water.
Yield 82%; white solid; mp: 260◦C; 1H NMR: 3.14 (d, 4H, 2JHP = 11.87 Hz, N-CH2-P),
1
3.46–3.49 (m, 8H, N-CH2); 13C NMR: 53.11, 56.12 (d, JCP = 133.99 Hz, CH2-P); 31P
NMR: 9.41; IR (cm−1): 2930 (νOH), 1260 and 1240 (νP = O), 943 (νP-O).
1-(2-Aminoethyl)piperazine-N,N’,N’-tris(methanenephosphonic Acid)
(12)
1-(2-Aminoethyl)piperazine (1.29 g, 10 mmol), placed in a quartz tube with refrig-
erant, was added to a mixture of phosphorous acid (2.46 g, 30 mmol), water (3 mL), and
hydrochloric acid (3 mL). Then formaldehyde (4.5 mL, 60 mmol) was added, and the unit
was irradiated at 240 W for 15 min. The product precipitated directly in the tube; it was
filtered and washed with water. Yield 80%; white solid; mp: 171◦C; 1H NMR: 3.04 (m, 8H,
CH2-N), 3.19 (d, 2H, 2JHP = 11.50 Hz, CH2-P), 3.28 (d, 4H, 2JHP = 11.25 Hz, 2 CH2-P),
3.58 (s, 4H, CH2); 13C NMR: 49.80 (2 CH2-N), 51.25 (CH2-N), 53.69 (d, 1JCP = 130 Hz,
2 CH2-P), 53.81 (2 CH2-N), 53.90 (CH2-N), 55.20 (d, 1JCP = 129 Hz, CH2-P); 31P NMR:
7.69, 8.0.
1,10-Diazacyclooctadecane-N,N’-bis(methanephosphonic Acid) (13)
A mixture of 1,10-diazacyclooctadecane (0.26 mL, 1 mmol), phosphorous acid
(0.16 g, 2 mmol), water (0.3 mL), and hydrochloric acid (36%, 0.3 mL) was irradiated
at 200 W for 5 min. Formaldehyde (3 mL, 40 mmol) was added rapidly, and the mixture
was irradiated at 240 W for 16 min. After cooling and evaporation, the precipitate was fil-
tered, and the white solid was washed with water and acetone. Yield 70%; mp: 261–263◦C;
2
3
1H NMR: 3.59 (d, JPH = 11.95 Hz; 4H, N-CH2-P), 3.95 (t, JHH = 5.47 Hz, 8H), 4.04

SYNTHESIS OF POLY(AMINOMETHYLENEPHOSPHONIC) ACIDS
2517
(s, 8H), 4.20 (t, 3JHH = 5.39 Hz, 8H); 13C NMR: 48.33 (d, 1JCP = 137.60 Hz, N-CH2-P),
53.19, 62.20, 68.35; 31P NMR: 7.52; IR (cm−1): 3151 (νOH), 2342 (νP = O), 1132 (νP = O),
1052 (νC-O), 964 (νP-O).
1,2-Diaminocyclohexane-N,N,N’,N’-tetrakis(methanenephosphonic)
Acid (14)
A mixture of 1,2-diaminocyclohexane (1.14 g, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated in a glass
cylinder reactor fitted with a cooler at 200 W for 5 min. After this, formaldehyde (6 mL,
80 mmol) was added rapidly, and the mixture was irradiated for 12 min at 240 W. After
cooling and evaporation, the precipitate was crystallized with acetonitrile, and the white
solid washed with water. Yield 71%; mp: 260◦C; 1H NMR: 2.12 (qt, 3JHH = 7.20 Hz, 4H),
2.55 (q, 3JHH = 7.12 Hz, 4H), 3.56 (d, 2JHP = 11.30 Hz, 8H, N-CH2-P), 3.44 (t, 3JHH
6.9 Hz, 2H); 13C NMR: 22.37, 48.80, 49.25 (d, 1JCP = 150 Hz, N-CH2P), 51.60 (d, 1JCP
=
=
145 Hz, N-CH2-P), 60.39; 31P NMR: 13.59 and 15.0; IR (cm−1): 2980 (νOH), 2352 (νP = O),
1092 (νP = O), 1018 and 942 (νP-O).
2,2-Diaminopropane-N,N,N’,N’-tetrakis(methanenephosphonic Acid)
(15)
A mixture of 2,2-diaminopropane (0.85 mL, 10 mmol), phosphorous acid (3.28 g,
40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated in a glass
cylinder reactor fitted with a cooler at 240 W for 2 min. After this, formaldehyde (6 mL,
80 mmol) was added rapidly, and the mixture was irradiated for 28 min at 240 W. After
cooling and evaporation, the precipitate was crystallized from acetonitrile/methanol (1:1).
1
2
Yield 43%; mp: 138◦C; H NMR: 1.35 (s, 3H), 1.73–1.77 (m, 3H), 3.12 (d, JHP = 11.0
Hz, 8H, N-CH2-P); 13C NMR: 13.51, 17.09, 30.0, 50.10 (d, JCP = 138.70 Hz, CH2-P);
1
31P NMR: 8.79; IR (cm−1): 2750 (νOH), 1324 (νP-OH), 1120 (νP = O), 1015 and 966 (νP-O).
1,4-Bis(aminomethyl)benzene-N,N’-bis(methanephosphonic Acid) (16)
A mixture of 1,4-bis(aminomethyl)benzene (1.36g, 10 mmol), phosphorous acid
(3.28 g, 40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated in a
glass cylinder reactor fitted with a cooler at 240 W for 1 min. After this, formaldehyde
(6 mL, 80 mmol) was added rapidly, and the mixture was irradiated for 12 min at 240 W.
After cooling and evaporation, the precipitate was filtered, and the white solid was washed
1
2
with water. Yield 93%; mp: 260◦C; H NMR: 3.50 (d, JHP = 11.37 Hz, 8H, N-CH2-P),
4.98 (s, 4H, N-CH2-Ar), 7.90 (s, 4H, Har); 13C NMR: 51.57 (d, 1JCP = 131.20 Hz, N-CH2-
P), 57.44 (CH2-N), 129.87 and 159.20 (Car); 31P NMR: 6.64; IR (cm−1): 3023 (νOH), 2343
(νP = O), 1484 (νC = C), 1167 (νP = O), 952 (νP-O), 684 and 774 (νCH).
1,3-Bis(aminomethyl)benzene-N,N’-bis(methanephosphonic Acid) (17)
A mixture of 1,3-bis(aminomethyl)benzene (1.36 g, 10 mmol), phosphorous acid
(3.28 g, 40 mmol), water (3 mL), and hydrochloric acid (36%, 3 mL) was irradiated in
a glass cylinder reactor at 240 W for 2 min. After this, formaldehyde (6 mL, 80 mmol)
was added rapidly, and the mixture was irradiated for 12 min at 240 W. After cooling

2518
D. VILLEMIN ET AL.
and evaporation, the precipitate was filtered, and the white solid was washed with acetone
1
2
and water. Yield 46%; H NMR: 3.17 (d, JHP = 11.30 Hz, 8H, N-CH2-P), 4.6 (s, 4H,
N-CH2-Ar), 7.52–7.57 (m, 4H, Har); 31C NMR: 51.50 (d, JCP = 131.0 Hz, N-CH2-P),
1
59.39 (CH2-N), 130.31 and 133.79 (Car); 31P NMR: 6.79.
1,2-Bis(aminomethyl)benzene-N,N’-bis(methanephosphonic Acid) (18)
A mixture of 1,2-bis(aminomethyl)benzene (0.395 g, 1.86 mmol), phosphorous acid
(0.62 g, 7.44 mmol), water (2 mL), and hydrochloric acid (36%, 2 mL) was irradiated at
210 W for 2 min. After this, formaldehyde (1.2 mL, 15 mmol) was added rapidly, and the
mixture was irradiated at 210 W for 8 min. After cooling and evaporation, the precipitate
was filtered, and the yellow solid was washed with water and 2-propanol. Yield 68%; mp:
1
2
240◦C; H NMR: 2.20 (s, 4H, N-CH2-Ar), 3.21 (d, 8H, JHP = 11.25 Hz, N-CH2-P),
7.34–7.62 (m, 8H, Har); 13C NMR: 52.21 (d, 1JCP = 125.0 Hz, N-CH2-P), 59.79 (CH2-N),
127.33; 127.70; 129.21; 130.09; 132.31; 137.20; 138.81 and 142.22 (Car); 31P NMR: 6.69;
IR (cm−1): 3000–2850 (νP-OH), 1455 (νCH2), 1143 (νP = O), 1010 and 930 (νP-O).
1-Amino-3-ethylaminopropane-N,N,N’-tris(methanenephosphonic
Acid) (19)
1-Amino-3-ethylaminopropane (2.04 g, 20 mmol), placed in a quartz tube with re-
frigerant, was added to a mixture of phosphorous acid 4.92g (60 mmol), water (2 mL),
and hydrochloric acid (6 mL). Formaldehyde (9 mL, 120 mmol) was then added, and the
unit was irradiated at 240 W for 15 min. After cooling and evaporation, the precipitate was
1
filtered, and the white solid was washed with 2-propanol. Yield 80%; H NMR: 0.83 (t,
3JHH = 7.0 Hz, 3H, CH3), 1.77–1.81 (m, 2H, CH2), 2.88–2.91 (m, 6H, CH2-N) 3.12 (d,
2JHP = 12.75 Hz, 6H, N-CH2-P); 13C NMR: 7.70 (CH3), 18.01 (CH2), 41.89 (CH2-N),
48.10 (d, 1JCP = 138.30 Hz, CH2-P), 50.70 (d, 1JCP = 136.50 Hz, CH2-P), 52.59 (CH2-N);
31P NMR: 8.31 and 8.78.
1-Amino-3-methylaminopropane-N,N’,N’-tris(methanenephosphonic
Acid) (20)
1-Amino-3-methylaminopropane (0.88 g, 10 mmol), placed in a quartz tube with
refrigerant, was added to a mixture of phosphorous acid (2.46 g, 30 mmol), water (3 mL),
and hydrochloric acid (3 mL). Formaldehyde (4.5 mL, 60 mmol) was then added, and the
unit was irradiated for 12 min at 240 W. After cooling and evaporation, a white solid was
1
obtained after crystallization with 2-propanol and filtration. Yield 74%; mp: 220◦C; H
2
NMR: 1.93–1.97 (m, 3H, CH3-N), 2.75 (s, 4H, CH2-N), 2.90 (d, JHP = 12.70 Hz, 2H,
N-CH2-P), 3.05 (d, 2JHP = 12.70 Hz, 4H, N-CH2-P), 3.23–3.27 (m, 2H). 13C NMR: 18.78
(CH3-N), 42.51 (CH2), 51.35 (d, 1JCP = 138.30 Hz, CH2-P), 52.20 (d, 1JCP = 138.30 Hz,
CH2-P), 54.19 (CH2-N). 31P NMR: 6.11 and 6.70; IR (cm−1): 3000–2850 (νP-OH), 1466
(νCH2), 1160 (νP = O), 920 (νP-O).
Ethyleneimine-N-methanephosphonic Acid Polymer (21)
ꢀR
Different polyethyleneimines were used such as Lupasol (BASF) G2O (1.3kDa),
WF (25 kDa), P (750 kDa), SK (2000 kDa). For example Lupasol (BASF) WF: average

SYNTHESIS OF POLY(AMINOMETHYLENEPHOSPHONIC) ACIDS
2519
molecular weight 25000; average motives (C2H6N) = 581; structure dendritic NH2/NH/N =
1/1.20/0.76. To polyethyleneimine (1.72 g, 50% in water, 20 mequ) placed in a quartz
tube with cooler, a mixture of phosphorous acid (1.64 g, 20 mmol), water (2 mL), and
hydrochloric acid (2 mL) was added. The mixture was irradiated for 8 min at 175 W. Then
formaldehyde (3.3 mL, 40 mmol) was added. The solution was dialyzed with water. After
1
evaporation, the polymer was obtained. Yield 90%; Tg: 122◦C; H NMR: 2.80–3.40 (m,
CH2-N); 13C NMR: 43.0–45.60 (m, N-CH2-P), 47.60–51.60 and 50.60–54.60 (m, CH2-P);
31P NMR: 7.80; IR (cm−1): 2340 (νP-OH), 1110 (νP = O), 1030 (νP-O). Anal. for the ideal
linear polymer (C3H8NO3P)x calcd.: C 26.29; H 5.88; N 10.22%, found: C 27.08; H 7.25;
N 11.16%.
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