Synthesis and characterization of new organic phosphonates monomers as flame retardant additives for polymers

Article abstract of DOI:10.1080/10426500701290748

Commercially available polyphenols react with diethylphosphite to give polyphosphonates, which are easily transformed by LDA in good yields to polyorthohydroxy aryl phosphonates. Moreover, some bis-benzyl aminobenzyl phosphonates have been prepared in good yields. These new monomers are of great relevance for the synthesis of thermal resistant polycondensates containing phosphonate moieties.

Full text of DOI:10.1080/10426500701290748

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Phosphorus, Sulfur, and Silicon
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Synthesis and Characterization
of New Organic Phosphonates
Monomers as Flame Retardant
Additives for Polymers
Paolo Finocchiaro a , Giuseppe A. Consiglio a ,
Andrea Imbrogiano a & Salvatore Failla a
a Dipartimento di Metodologie Fisiche e Chimiche
per l'Ingegneria, Facoltà di Ingegneria , Università di
Catania , Catania, Italy
Published online: 15 Jun 2007.
To cite this article: Paolo Finocchiaro , Giuseppe A. Consiglio , Andrea Imbrogiano &
Salvatore Failla (2007) Synthesis and Characterization of New Organic Phosphonates
Monomers as Flame Retardant Additives for Polymers, Phosphorus, Sulfur, and Silicon
and the Related Elements, 182:8, 1689-1701, DOI: 10.1080/10426500701290748
To link to this article: http://dx.doi.org/10.1080/10426500701290748
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Phosphorus, Sulfur, and Silicon, 182:1689–1701, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701290748
Synthesis and Characterization of New Organic
Phosphonates Monomers as Flame Retardant Additives
for Polymers
Paolo Finocchiaro
Giuseppe A. Consiglio
Andrea Imbrogiano
Salvatore Failla
Dipartimento di Metodologie Fisiche e Chimiche per l’Ingegneria,
Facolta` di Ingegneria, Universita` di Catania, Catania, Italy
Commercially available polyphenols react with diethylphosphite to give polyphos-
phonates, which are easily transformed by LDA in good yields to polyorthohydroxy
aryl phosphonates. Moreover, some bis-benzyl aminobenzyl phosphonates have been
prepared in good yields. These new monomers are of great relevance for the synthesis
of thermal resistant polycondensates containing phosphonate moieties.
Keywords Aryl-amine phosphates; environmental friendly additives; NMR and FAB-
MS characterizations; poly-hydroxy aryl phosphates
INTRODUCTION
The fire resistance of polymeric materials is an extremely important
problem, and generally, a large volume of additives is used for enhanc-
ing the fire safety performance. Of course, such additives should have a
low impact on the physical properties of the materials and a low produc-
tion cost. Up to now, the most commonly used additives are halogenated
compounds, which are very effective in reducing the heat release rate
of commercial polymers, but on the other hand, they present a highly
dangerous environmental impact, especially during the process of recy-
cling and incineration. Halogen-based compounds combined with some
other additives (i.e., Sb2O3) are still widely used as fire retardants,
Received December 29, 2005; accepted February 1, 2007.
We thank the Ministero dell’Istruzione, dell’Universita` e della Ricerca (MIUR) for
financial support.
Address correspondence to Salvatore Failla, Dipartimento di Metodologie Fisiche e
Chimiche per l’Ingegneria, Facolta` di Ingegneria, Universita` di Catania, Viale A. Doria,
6. I-95125 Catania, Italy. E-mail: sfailla@dmfci.unict.it
1689

1690
P. Finocchiaro et al.
in particular for composite organic polymers such as phenolic resins,
epoxide or bismaleimide resins.1 However, when burning they gener-
ally release halogen acids and metal halides; the proven efficiency of
these additives has to be balanced against this formation of undesired,
corrosive, and obscuring fumes.2 Furthermore, halogenated flame re-
tardants may form extremely toxic dibenzodioxines, and the toxicity of
antimony trioxide should be taken into account for this handling and
use.3 The important problem today, therefore, is whether the flame re-
tardants are suited to satisfy a low environmental impact, or if it is
wise to consider the development of alternative products.
It is generally recognized that flame retardants, which contain phos-
phorus or phosphonates, have substantial advantages compared to the
more used halogenated phosphate esters and the brominated polyols.
Halogen-free materials for electronic devices with new flame retardant
principles based on nitrogen and phosphorus structures have been de-
veloped by Kettrup et al.4 and optimized in order to satisfy low envi-
ronmental impact.
Toxicity tests with the Daphnia Magna Test5 indicate the lowest
toxicity for materials containing only phosphorus as flame retardant
and aluminum oxide hydroxide as filling. Furthermore, no neurotoxic
compounds were formed during the combustion on flame. In this case,
the typical intumescent system composition consists of a source of char
(polyhydric compound), a source of phosphonic acid (which promotes the
charring process), and a spumific compound, usually amines/amides,
which evolve gaseous products on heating, may contribute to blow the
char.6−10 Other typical intumescent systems are built into the basic
resin. For example, special epoxy resins act as carbonifics, thus partially
contributing to the build up of the char, and novel intumescent epoxy
systems have been prepared by the reaction of phosphorus-containing
compounds with different epoxy resins.
M. R. Buckingam et al.11−13 have studied more than 20 novel
phosphorylated monomers as flame retardants cross-linkable in
epoxy resins. Other phosphorus-based dual-function materials, act-
ing both as flame retardant and as curing agents, have been stud-
ied. Bis(m-aminophenyl)methylphosphine oxide (BAMPO) was found
to act as curing agent, mixed in certain percentage to the 4,4ꢀ-
diaminodiphenylsulphone (DDS), for the epoxy resins TGDDM and
DGEBA. Furthermore, these resins cured with BAMPO, show a higher
resistance to the fire compared to the same resins cured with only
DDS.14,15
Imparting flame resistance into epoxy resins can be achieved not only
using fire-resistant curing agents but also using phosphorus-containing
oxiranes.16−20 Ying-Ling et al.16 have synthesized bis-glycidyl

New Organic Phosphonates
1691
phenylphosphate (BGPP), a new phosphorus-containing oxirane. This
compound was prepared by a simple synthesis and has high phosphorus
content, being very effective in flame retardation.
Considering the great interest in phosphorus containing compounds
as antiflammable agents, we decided to synthesize a great variety of
phosphonates, which could be used as hardeners in the curing process
of thermosetting epoxy resins to limit the flammability of the result-
ing system. Futhermore, our systems are suitable as monomers for
obtaining polycondensates, which contain the phosphonate moiety in
polymeric chain.
RESULTS AND DISCUSSION
In a previous paper,21 we reported the syntheses of new phosphonated
derivatives of bis-phenols and used them to reduce flammability of ther-
mosetting DGEBA epoxy resin.22 As these phosphonated phenols are
very interesting as additive for polymeric materials, we decided to syn-
thesize tris and tetrakis phosphonated derivatives of phenol (Scheme 1).
For the synthesis of the phosphonates, suitable for polymer chemistry,
we used compounds with three and four phenol units, which were
SCHEME 1

1692
P. Finocchiaro et al.
transformed into the corresponding diethyl phosphates by treatment
with diethyl phosphite in CCl4 as solvent in the presence of triethy-
lamine as base. After isolation, the crude phosphates were transformed
into the corresponding phosphonates 3 and 4 by lithium diisopropy-
lamide (LDA) at –78◦C, trough [1,3]-sigmatropic rearrangement that
involve the fission of an oxygen-phosphorus bond, and the formation of
a new carbon-phosphorus bond. The procedure used is an adaptation of
the reaction reported first by Dhawan and Redmore.23 We have found,
that this procedure gives good yields also in the case of polyhydroxy
compounds 1 and 2.
In the Experimental section, we report the full characterization of
compounds 3 and 4, including their NMR data. In the proton, as well
as in the phosphorus NMR spectra, all chemical shifts fall into the
expected range.
Commonly used epoxy resin formulations are obtained by mixing
of oligomers based on diglycid ether of bisphenol A (DGEBA) and aro-
matic or aliphatic amines as curing agents. Considering that amines are
the most used curing agents for epoxy resin systems, we also decided
to prepare phosphonate derivatives containing NH groups, in order to
help curing process and to bind the fire-retardant additive to the final
polymeric material.
Our approach to the synthesis of phosphorus-containing or-
ganic compounds consists in using commercially available diethyl
(4-aminobenzyl)phosphonate (compound 7, Scheme 3) and a corre-
sponding aldehyde. Suitable aldehydes are prepared by reacting
4-hydroxybenzaldehyde 5 with a bis-, tris- or tetrakis-halomethyl
derivative. An example is represented by compounds 6h and 6i,
which contain three and four aldehyde groups in the same molecule,
respectively (Scheme 2).
The syntheses of the phosphonates were performed by reacting the
amine 7 with the corresponding aldehyde 6a-i in toluene using a Dean-
Stark apparatus; the Schiff bases thus obtained were reduced directly
with NaBH4 in EtOH after the toluene was removed in vacuo (Scheme
3). The products were isolated from the reaction mixture by pouring it
in water and filtering the solid or extracting the oil thus obtained to
give compounds 8a–i in good yields.
Similarly, bis-aldehydes 9 and 10 were prepared by Duff reaction
(Scheme 4) from the related bis-phenols by reacting the phenol with
hexamethylenetetramine (HMTA) in acetic acid at 120◦C. The reaction
mixture was then reacted with H2SO4 and H2O to destroy the interme-
diate and poured into water. The resulting solid was filtered, washed
with water, and crystallized from methanol to give bis-aldehydes 9 and
10 in moderate yields (40–50%).

New Organic Phosphonates
1693
SCHEME 2
SCHEME 3

1694
P. Finocchiaro et al.
SCHEME 4
Reaction of these compounds with amine 7 yields the aminophenol
derivatives 11 and 12, respectively (Scheme 4).
Now, we dispose of a large variety of reactive molecules containing
one or more phosphonate groups. Bis or polyhydroxy derivatives can
be used as fire-retardant blocks in the synthesis of high-performance
engineering polymers such as PEK, PES, PEES, PEEK, PC, and so on.
The compounds containing reactive NH groups can be useful for the
preparation of epoxy resins possessing reduced flammability.
EXPERIMENTAL
All reactions were performed under an inert atmosphere of nitrogen.
Acetonitrile was dried by distillation from calcium hydride under nitro-
gen. All the other solvents were used without any purification. Unless
otherwise stated commercial chemicals were used as supplied. Com-
pound 2 was prepared according to a published procedure.24 1H, 13C, and
31P NMR spectra were recorded on a Varian-Inova 500 MHz instrument

New Organic Phosphonates
1695
operating at 500 MHz, 125 MHz, and 200 MHz, respectively, us-
ing TMS as internal reference (1H, 13C) and 85% H3PO4 as external
reference(31P). Mass spectra were obtained using a double-focusing
Kratos MS 50S instrument equipped with a standard FAB source
and DS 90 data system using 3-nitro-benzylalcohol as matrix. Melt-
ing points were determined on a Bu¨chi 530 melting point apparatus
and are uncorrected.
General Synthetic Procedure for Compounds 6a–i
A suspension of p-hydroxybenzaldehyde 5 (10 mmol), an equivalent
amount of the corresponding halogen derivative, and potassium carbon-
ate (20 mmol) in CH3CN (20 mL) was refluxed overnight. The reaction
mixture was poured into water, the solid thus obtained was filtered,
and washed with water and cold methanol. The white solid was recrys-
tallized or triturated from methanol to give compounds 6a–i as white
needles (yield ∼ 75%). Physical properties of compounds 6a,25 6b26 and
6e,27 6g27 are the same as those reported in literature.
General Synthetic Procedure for Compounds 8a-i and 11–12
A solution of aldehyde 6a–i (2 mmol) and an equivalent amount of di-
ethyl (4-aminobenzyl)phosphonate 7 were azeotropically distilled with
toluene (20 mL) for 3 h. After cooling, the toluene was removed under
vacuum and the residue dissolved in ethanol (10 mL). NaBH4 (8 mmol)
was added and the mixture stirred overnight at room temperature. The
solvent was evaporated under reduced pressure and the residue was
extracted with chloroform/water. The organic phase was washed with
water, dried over Na2SO4, and concentrated to give amines 8a–i and11,
12 as a white powder or a yellow oil.
Compound 3
1H NMR (CDCl3)δ: 10.12 (s, 3H, ArOH), 7.15 (dd, 3 J = 8.5 Hz,
4 J = 2.5 Hz, 3H, ArH), 6.97 (dd, 3 J = 15.5 Hz, 4 JHH = 2.5 Hz,
HH
PH
HH
3H, ArH), 6.87 (dd, 4 J = 7.5 Hz, 3 J = 8.5 Hz, 3H, ArH), 4.12–3.93
PH
HH
3
(m, 12H, POCH2CH3), 2.07 (s, 3H, CH3), 1.23 (t, J = 7.0 Hz, 18H,
HH
POCH2CH3). 13C NMR (CDCl3) δ: 160.4, 139.5, 135.2, 130.9, 117.4,
108.4 (1 J = 179.1 Hz), 62.7, 50.4, 30.3, 16.1. 31P NMR (CDCl3) δ: 22.4.
PC
FAB MS (%): m/z 715.3 (100%) [M+H]+, m/z 737.2 (15%) [M+Na]+.
White crystals; m.p. = 169–171◦C; yield 62%.

1696
P. Finocchiaro et al.
Compound 4
1H NMR (DMSO-d6, 70 ◦C) δ: 9.95 (s, 4H, ArOH), 7.27 (m, 8H, ArH),
6.83 (m, 4H, ArH), 4.06-3.99 (m, 16H, POCH2CH3), 2.19 (broad s, 8H,
◦
ring-CH2), 1.18 (m, 24H, POCH2CH3). 31P NMR (DMSO-d6, 50 C) δ:
20.3. FAB MS (%): m/z 997.3 (35%) [M+H]+. White crystals; m.p. =
216–217◦C; yield 65%.
Compound 6c
1H NMR (CDCl3) δ: 9.89 (s, 2H, ArCHO), 7.85 (d, 3 J = 8.5 Hz,
HH
3
4H, ArH), 7.27 (s, 2H, ArH), 7.05 (d, J = 8.5 Hz, 4H, ArH), 5.10 (s,
HH
4H, ArCH2O), 2.36 (s, 6H, CH3). 13C NMR (CDCl3) δ: 190.7, 163.7,
134.4, 134.0, 132.0, 130.9, 130.2, 115.0, 68.5, 18.4. FAB MS (%): m/z
375.5 (34) [M + H]+. White crystals; m.p. = 180–183◦C; yield 80%.
Compound 6d
1H NMR (CDCl3) δ: 9.88 (s, 2H, ArCHO), 7.84 (d, 3 J = 8.5 Hz, 4H,
ArH), 7.41 (s, 1H, ArH), 7.13 (s, 1H, ArH), 7.05 (d, J HH= 8.5 Hz, 4H,
3
HH
ArH), 5.09 (s, 4H, ArCH2O), 2.36 (s, 6H, CH3). 13C NMR (CDCl3) δ:
190.7, 163.7, 137.3, 133.0, 131.9, 131.6, 130.1, 129.3, 115.0, 68.5, 18.5.
FAB MS (%): m/z 375.4 (44) [M + H]+. White crystals; m.p. = 130–133◦C;
yield 84%.
Compound 6f
1H NMR (CDCl3) δ: 9.88 (s, 2H, ArCHO), 7.86 (d, 3 J = 8.5 Hz,
HH
3
4H, ArH), 7.13 (d, J = 8.5 Hz, 4H, ArH), 7.04 (s, 1H, ArH), 5.15 (s,
HH
4H, ArCH2O), 2.40 (s, 9H, CH3). 13C NMR (CDCl3) δ: 190.7, 164.1,
138.9, 132.0, 130.7, 130.5, 130.1, 114.8, 65.1, 19.7, 15.3. FAB MS (%):
m/z 389.4 (65) [M + H]+. White crystals; m.p. = 134–135◦C; yield 78%.
Compound 6h
1H NMR (CDCl3) δ: 9.91 (s, 3H, ArCHO), 7.87 (d, 3 J = 8.5 Hz, 6H,
HH
3
ArH), 7.14 (d, J = 8.5 Hz, 6H, ArH), 5.22 (s, 6H, ArCH2O), 2.46 (s,
HH
9H, CH3). 13C NMR (CDCl3,) δ: 190.7, 163.9, 139.7, 132.0, 131.2, 114.8,
65.2, 16.0. FAB MS (%): m/z 475.6 (34) [M + H]+. White crystals; m.p.
= 169–170◦C; yield 82%.
Compound 6i
1H NMR (CDCl3) δ: 9.84 (s, 4H, ArCHO), 7.81 (d, 3 J = 8.5 Hz,
HH
3
8H, ArH), 7.30 (s, 2H, ArH), 7.19 (d, J = 8.5 Hz, 8H, ArH), 5.38 (s,
HH
8H, ArCH2O). FAB MS (%): m/z 615.6 (77) [M + H]+. White crystals;
m.p. = 194–196◦C; yield 41%.

New Organic Phosphonates
1697
Compound 8a
1H NMR (CDCl3) δ: 7.30 (d, 3 J = 9.0 Hz, 4H, ArH), 7.09 (dd,
HH
3 J = 9.0 Hz, 4 J = 2.5 Hz, 4H, ArH), 6.85 (d, 3 J = 9.0 Hz, 4H,
HH
PH
HH
ArH), 6.58 (d, 3 J = 9.0 Hz, 4H, ArH), 4.22 (s 4H, ArCH NH), 4.02 (m,
HH
2
8H, POCH CH3), 3.96 (t, 3 J = 6.5 Hz, 4H, ArOCH CH2CH2), 3.04
2
HH
2
(d, 2 J = 21.0 Hz, 4H, ArCH2P), 1.81 (m, 4H, ArOCH2CH CH2), 1.53
PH
2
(m, 4H, ArOCH2CH2CH ), 1.21 (t, 3 J = 7.0 Hz, 12H, POCH2CH ).
2
HH
3
13C NMR (CDCl3) δ: 158.4, 146.7, 130.9, 130.5, 128.9, 121.2, 114.6,
113.3, 67.8, 62.0, 48.1, 33.2 (d, 1 J = 138.1 Hz), 29.2, 25.8, 16.4. 31P
PC
NMR (CDCl3) δ: 27.5. FAB MS (%): m/z 781.9 (60) [M + H]+. White
crystals; m.p. = 106–107◦C; yield 87%.
Compound 8b
1H NMR (CDCl3) δ: 7.26 (d, 3 J = 8.5 Hz, 4H, ArH), 7.08 (dd,
HH
3 J = 8.5 Hz, 4 J = 2.5 Hz, 4H, ArH), 6.87 (d, 3 J = 8.5 Hz, 4H,
HH
HH
ArH), 6.58 (d, 3 J PH= 8.5 Hz, 4H, ArH), 4.25 (s, 4H, ArCH NH), 4.13
HH
2
(t, 3 J = 6.0 Hz, 4H, ArOCH CH2), 4.02 (m, 8H, POCH CH3), 3.03
HH
2
2
(d, 2 J = 21.0 Hz, 4H, ArCH2P), 2.25 (quint, 3 J = 6.0 Hz, 2H,
PH
HH
ArOCH2CH ), 1.24 (t, 3 J = 7.0 Hz, 12H, POCH2CH ). 31P NMR
2
HH
3
(CDCl3) δ: 27.4. FAB MS (%): m/z 739.3 (56) [M + H]+; yield 81%.
Compound 8c
1H NMR (CDCl3) δ: 7.30 (d, 3 J = 8.5 Hz, 4H, ArH), 7.09 (dd,
HH
3 J = 8.5 Hz, 4 J = 2.5 Hz, 4H, ArH), 6.98 (d, 3 J = 8.5 Hz, 4H,
HH
PH
HH
3
ArH), 6.59 (d, J = 8.5 Hz, 4H, ArH), 5.03 (s, 4H, ArCH2O), 4.25 (s,
HH
4H, ArCH NH), 4.00 (m, 8H, POCH CH3), 3.03 (d, 2 J = 21.0 Hz, 4H,
2
2
PH
ArCH2P), 2.33 (s, 6H, ArCH3), 1.24 (t, 3 J = 7.0 Hz, 12H, POCH2CH ).
FAB MS (%): m/z 843.9 (76) [M + H]+. White crystals; m.p. = 163–165◦3C;
HH
yield 91%.
Compound 8d
3
1H NMR (CDCl3) δ: 7.41 (s, 1H, ArH), 7.27 (d, J = 8.5 Hz, 4H,
HH
ArH), 7.09 (dd, 3 J = 8.5 Hz, 4 J = 2.5 Hz, 4H, ArH), 7.08 (s, 1H,
HH
PH
ArH), 6.95 (d, 3 J = 8.5 Hz, 4H, ArH), 6.58 (d, 3 J = 8.5 Hz, 4H, ArH),
HH
HH
4.99 (s, 4H, ArCH2O), 4.23 (s, 4H, ArCH NH), 4.00 (m, 8H, POCH CH3),
2
2
3.03 (d, 2 J = 21.0 Hz, 4H, ArCH2P), 2.33 (s, 6H, ArCH3), 1.23 (t,
PH
3 J = 7.0 Hz, 12H, POCH2CH ). 13C NMR (CDCl3) δ: 158.2, 147.0,
HH
3
137.0, 132.8, 132.4, 131.5, 130.5, 129.6, 128.5, 119.9, 114.9, 113.1, 68.4,
61.9, 47.9, 33.2 (d, J = 138.1 Hz), 18.5, 16.7. 31P NMR (CDCl3) δ:
1
PC
27.6. FAB MS (%): m/z 829.9 (69) [M + H]+. White crystals; m.p. =
123–124◦C; yield 80%.

1698
P. Finocchiaro et al.
Compound 8e
1H NMR (CDCl3) δ: 7.44 (d, 3 J = 8.5 Hz, 4H, ArH), 7.26 (d,
HH
3 J = 8.5 Hz, 4H, ArH), 7.08 (dd, 4 J = 2.5 Hz, 4H, ArH), 6.98 (d,
HH
PH
3 J = 8.5 Hz, 4H, ArH), 6.52 (d, 3 J = 8.5 Hz, 4H, ArH), 5.08 (s, 4H,
HH
HH
ArOCH2), 4.23 (s, 4H, ArCH NH), 3.98 (m, 8H, POCH CH3), 3.03 (d,
2
2
2 J = 21.0 Hz, 4H, ArCH2P), 1.23 (t, 3 J = 7.0 Hz, 12H, POCH2CH ).
PH
HH
3
13C NMR (CDCl3) δ: 158.0, 147.0, 136.7, 131.7, 130.5, 128.8, 127.6,
119.9, 114.9, 113.0, 69.7, 61.9, 47.8, 33.2 (1 J = 138.1 Hz), 16.3. 31P
PC
NMR (CDCl3) δ: 27.7. FAB MS (%): m/z 1205.3 (56) [M + H]+; yield
70%.
Compound 8f
1H NMR (CDCl3) δ: 7.31 (d, 3 J = 8.5 Hz, 4H, ArH), 7.08 (dd,
HH
3 J = 8.5 Hz, 4 J = 2.5 Hz, 4H, ArH), 7.01 (s, 1H, ArH), 6.97 (d,
HH
PH
3 J = 8.5 Hz, 4H, ArH), 6.57 (d, 3 J = 8.5 Hz, 4H, ArH), 5.05 (s, 4H,
HH
HH
ArCH2O), 4.25 (s, 4H, ArCH NH), 4.00 (m, 8H, POCH CH3), 3.02 (d,
2
2
2 J = 21.0 Hz, 4H, ArCH2P), 2.41 (s, 3H, ArCH3), 2.38 (s, 6H, ArCH3),
PH
1.23 (t, 3 J = 7.0 Hz, 12H, POCH2CH ). 13C NMR (CDCl3) δ: 158.5,
HH
3
146.9, 138.5, 131.5, 131.2, 130.5, 130.4, 128.8, 114.9, 113.1, 65.9, 61.9,
1
47.9, 33.2 (d, J = 138.1 Hz), 19.7, 16.4, 15.2. 31P NMR (CDCl3) δ:
CP
27.7. FAB MS (%): m/z 801.9 (63) [M + H]+; yield 97%.
Compound 8g
1H NMR (CDCl3) δ: 7.49 (s, 1H, ArH), 7.38 (m, 3H, ArH), 7.27 (d,
3 J = 8.5 Hz, 4H, ArH), 7.08 (dd, 4 J = 2.5 Hz,3 J = 8.5 Hz, 4H,
HH
PH
ArH), 6.94 (d, 3 J = 8.5 Hz, 4H, ArH), 6.57 (d, 3 J =H8H.5 Hz, 4H, ArH),
HH
HH
5.06 (s, 4H, ArCH2O), 4.22 (s, 4H, ArCH NH), 4.00 (m, 8H, POCH CH3),
2
2
3.02 (d, 2 J = 21.0 Hz, 4H, ArCH2P), 1.23 (t, 3 J = 7.0 Hz, 12H,
PH
HH
POCH2CH ). 13C NMR (CDCl3) δ: 157.9, 146.8, 137.7, 131.7, 130.5,
3
130.4, 128.8, 126.9, 126.3, 119.8, 114.9, 113.1, 69.8, 61.7, 47.9, 33.2 (d,
1 J = 138.1 Hz), 16.4. 31P NMR (CDCl3) δ: 27.6. FAB MS (%): m/z
CP
801.9 (35) [M + H]+. White crystals; m.p. = 127–129◦C; yield 87%.
Compound 8h
1H NMR (CDCl3) δ: 7.30 (d, 3 J = 8.5 Hz, 6H, ArH), 7.09 (dd,
HH
3 J = 8.5 Hz, 4 J = 2.5 Hz, 6H, ArH), 6.98 (d, 3 J = 8.5 Hz, 6H,
HH
HP
HH
3
ArH), 6.58 (d, J = 8.5 Hz, 6H, ArH), 5.08 (s, 6H, ArCH O), 4.25 (s,
HH
2
6H, ArCH NH), 4.00 (m, 12H, POCH CH3), 3.02 (d, 2 J = 21.0 Hz, 6H,
2
2
HP
ArCH2P), 2.43 (s, 9H, ArCH3), 1.24 (t, 3 J = 7.0 Hz, 18H, POCH2CH ).
HH
3
13C NMR (CDCl3) δ: 158.2, 147.1, 139.2, 131.7, 131.6, 130.5, 130.4,
128.8, 114.6, 113.0, 64.9, 61.9, 47.8, 33.2 (d, 1 J = 138.1 Hz), 16.4,
CP

New Organic Phosphonates
1699
15.8. 31P NMR (CDCl3) δ: 27.6. FAB MS (%): m/z 1204.3 (42) [M +
H]+. Yield 82%.
Compound 8i
1H NMR (CDCl3) δ: 7.30 (d, 3 J = 8.5 Hz, 8H, ArH), 7.15 (s,
HH
2H, ArH), 7.09 (dd, 4 J = 2.5 Hz,3 J = 8.5 Hz, 8H, ArH), 6.98 (d,
PH
3 J = 8.5 Hz, 8H, ArH), 6.60 (d, 3 J H=H 8.5 Hz, 8H, ArH), 5.08 (s, 8H,
HH
HH
ArCH2O), 4.26 (s, 8H, ArCH NH), 4.00 (m, 16H, POCH CH3), 3.03 (d,
2
2
2 J = 21.0 Hz, 8H, ArCH2P), 1.24 (t, 3 J = 7.0 Hz, 24H, POCH2CH ).
PH
HH
3
13C NMR (CDCl3) δ: 158.7, 144.7, 139.5, 134.1, 129.9, 128.1, 127.5,
121.2, 114.2, 113.4, 69.6, 62.0, 47.2, 33.3 (1 J = 138.1 Hz), 16.5. 31P
CP
NMR (CDCl3) δ: 27.7. FAB MS (%): m/z 1524.6 (56) [M + H]+; yield
88%.
Compound 9
1H NMR (CDCl3) δ: 11.18 (s, 2H, ArOH), 9.84 (s, 2H, ArCHO), 7.28
(s, 4H, ArH), 7.19 (s, 4H, ArH), 2.21 (s, 6H, ArCH3), 1.68 (s, 6 H, CH3).
13C NMR (CDCl3) δ: 196.8, 158.3, 141.1, 137.0, 128.3, 126.8, 119.3,
41.5, 30.7, 15.2. FAB MS (%): m/z 313.1 (85%) [M+H]+. Yellowish pow-
der; m.p. = 140–141◦C; yield 45%.
Compound 10
1H NMR (CDCl3) δ: 12.01 (s, 2H, CHO), 9.56 (s, 2H, ArOH), 7.20 (s,
2
2
2H, ArH), 2.57 (d, J = 13.5 Hz, 2H, CH2), 2.37 (d, J = 13.5 Hz,
HH
HH
2H, CH2), 2.26 (s, 3H, CH3), 2.25 (s, 3H, CH3), 1.37 (s, 6H CH3), 1.35
(s, 6H, CH3). FAB MS (%): m/z 393.4 (25%) [M+H]+. Yellowish powder;
m.p. = 282–285◦C dec.; yield 44%.
Compound 11
1H NMR (CDCl3) δ: 7.14 (dd,3 J = 9.0 Hz, 4 J = 2.5 Hz, 4H,
HH
ArH), 6.96 (d,4 J = 2.0 Hz, 2H, ArH), 6.82 (d,4 J =P2H.0 Hz, 2H, ArH),
HH
HH
6.76 (d,3 J = 8.5 Hz, 4H, ArH), 4.30 (s, 4H, CH2NH), 4.04–3.97 (m, 8H,
HH
POCH2CH3), 3.06 (d, 2 J = 21.5 Hz, 4H, CH2P), 2.21 (s, 6H, ArCH3),
PH
1.62 (s, 6H, CH3), 1.25 (t, 3 J = 7.0 Hz, 12H, POCH2CH3). FAB MS
HH
(%): m/z 767.4 (50%) [M+H]+; yield 100%.
Compound 12
1H NMR (DMSO-d6) δ: 8.63 (s, 2H, ArOH), 6.91 (d,3 J = 8 Hz,
HH
4H, ArH), 6.90 (s, 2H, ArH), 6.28 (d,3 J = 8 Hz, 4H ArH), 5.15 (t,
HH
3 J = 5.5 Hz, 2H, NH), 3.94–3.91 (m, 8H, POCH2CH3), 3.68–3.32 (m,
HH
4H, CH2NH), 2.98 (d, 2 J = 21 Hz, 4H, CH2P), 2.28 (d, 2 J = 13 Hz,
PH
HH
2
2H, CH2), 2.27 (d, J = 13 Hz, 2H, CH2), 2.15 (s, 6H, CH3), 1.21 (s,
HH

1700
P. Finocchiaro et al.
6H, CH3), 1.14 (t, 3 J = 7 Hz, 12H, POCH2CH3), 1.09 (s, 6H, CH3)
HH
13C NMR (DMSO-d6) δ: 154.1, 147.2, 145.9, 142.3, 129.9, 128.3, 124.0,
123.0, 120.1, 119.7, 113.5, 61.2, 57.5, 43.7, 41.8, 40.6, 32.6, 31.4 (d,
1 J = 135.6 Hz) 29.7, 16.7, 16.2. 31P NMR (DMSO-d6) δ: 28.7. FAB
CP
◦
MS (%): m/z 847.3 (50%) [M+H]+. White crystals; m.p. = 199-202 C;
yield 96%.
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New Organic Phosphonates
1701
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