Efficient synthesis of bolaform- and gemini-type alkyl-bis-[(α-amino)phosphonocarboxylic or phosphonic acid] surfactants

Article abstract of DOI:10.1016/S0040-4020(02)00535-5

The synthesis of a new series of bolaform- and gemini-type phosphorus acid surfactants is described. The Pudovik addition reaction of P-H bond tetraoxyspirophosphoranes to symmetrical, prochiral bis-imines bearing different more or less long and rigid linkers occurs instantaneously at room temperature. This reaction is diastereoselective and quantitatively leads to the corresponding alkyl-bis-[α-aminospirophosphoranes] in good to high diastereomeric ratio. Selective and one-pot hydrolysis of these P^*-C^* bond bis-spirophosphoranes can be readily achieved either at room temperature by moist solvents giving the corresponding alkyl-bis-[α-aminophosphonocarboxylic acid] amphiphiles, or by a more drastic reaction of 20% aqueous hydrochloric acid under reflux affording free alkyl-bis-[α-aminophosphonic acid] surfactants in good yields.

Full text of DOI:10.1016/S0040-4020(02)00535-5

TETRAHEDRON
Pergamon
Tetrahedron 58 :2002) 5651±5658
Ef®cient synthesis of bolaform- and gemini-type alkyl-bis-
[ꢀa-amino)phosphonocarboxylic or phosphonic acid] surfactants
p
Karine Vercruysse-Moreira, Christophe Dejugnat and Guita Etemad-Moghadam
Â
 Ã
Laboratoire des IMRCP ꢀUMR 5623), Universite Paul Sabatier, 118 route de Narbonne-Bat. 2R1, 31062 Toulouse cedex 04, France
Received 10 January 2002; revised 8 May 2002; accepted 23 May 2002
AbstractÐThe synthesis of a new series of bolaform- and gemini-type phosphorus acid surfactants is described. The Pudovik addition
reaction of P±H bond tetraoxyspirophosphoranes to symmetrical, prochiral bis-imines bearing different more or less long and rigid linkers
occurs instantaneously at room temperature. This reaction is diastereoselective and quantitatively leads to the corresponding alkyl-bis-
[a-aminospirophosphoranes] in good to high diastereomeric ratio. Selective and one-pot hydrolysis of these Pp±Cp bond bis-spiro-
phosphoranes can be readily achieved either at room temperature by moist solvents giving the corresponding alkyl-bis-[a-aminophos-
phonocarboxylic acid] amphiphiles, or by a more drastic reaction of 20% aqueous hydrochloric acid under re¯ux affording free alkyl-bis-
[a-aminophosphonic acid] surfactants in good yields. q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
aggregates in aqueous media are also attractive for their
potential in various applications such as microencapsulation
and formulation of hydrophobic derivatives or drug
delivery,9 ion channels,10 catalysis,11 synthesis of nano-
materials,12 metal extraction,13 and so forth. Structurally
related to the bolaamphiphiles, the geminis :also called
dimeric surfactants), made of two identical amphiphilic
moieties connected at the level of the head groups by a
:¯exible or rigid) hydrophobic spacer, are known to form
a great variety of supramolecular structures such as
micelles, multilayers, rods, and vesicles, and appear to be
superior to their monomeric counterparts.14,15
During the last decades much work has been done to study
properties and functions of natural membranes.1 Membrane
lipids of thermophilic and acidophilic Archaebacteria,
particular microorganisms able to survive under drastic
conditions owing to the presence of very rigid membranes,
are constituted by natural bolaamphiphiles.2 Bolaamphi-
philes, so-called bolaforms, refer to a class of surfactant
molecules in which two hydrophilic head groups :neutral
or ionic) are connected by one or more hydrophobic linkers.
It has been shown that biological or synthetic bolaamphi-
philes self-organize into monolayer membranes which are
highly stable over time to the variation of temperature and
ionic strength changes.3 Thus, in order to understand the
properties that allow the support of such extreme environ-
mental conditions, and consequently, to prepare the stable
and heat-resistant membranous materials, the synthesis of a
large number of bolaamphiphiles :notably phosphorus deri-
vates) has been described.4,5 Their self-association studies
indicate that they are able to form micellar aggregates but
also vesicles, depending on the length of the hydrophobic
spacer.6,7 Moreover, it has been reported that the bolaforms
had no detergent effect on cell membranes and did not tend
to denature cells as the monocatenary compounds did.8
Furthermore, synthetic amphiphiles that form vesicular
The aim of the present work was to ®nd an ef®cient method
for the preparation of bolaform- and gemini-type phos-
phorus acid surfactants. We have recently described the
synthesis of new :a-hydroxyalkyl)- and :a-aminoalkyl)-
phosphinic and phosphonic acid amphiphiles by Pudovik
addition reaction of the P±H-labile phosphorus derivatives
on long-chain aldehydes and imines, respectively.16 These
a-functionalized phosphonic acids are isosteres of natural
aminoacids and have potential biological applications in
agrochemistry and in medicine.17 The molecular packing
of these derivatives depend markedly on the length
and the rigidity of the hydrophobic spacer and on the
nature of the polar heads. We report here the reactivity of
P±H bond spirophosphoranes towards bis-imines having
various long or short and ¯exible or rigid linkers, and
the one-pot and selective hydrolysis of the alkyl-bis-
[:a-amino)-spirophosphorane] intermediates to afford
bolaform- and gemini-type alkyl-bis-[:a-amino)-phos-
phonocarboxylic acid] oralkyl-bis [:a-amino)phosphonic
acid] amphiphiles.
Keywords: phosphorus acid surfactants; alkyl-bis-[:a-amino)phosphonic
acids]; alkyl-bis-[:a-amino)phosphonocarboxylic acids]; bolaform- and
gemini-type amphiphiles; spirophosphorane; Pudovik reaction.
Corresponding author. Tel.: 133-5-61-558333; fax: 133-5-61-558155;
e-mail: dejugnat@chimie.ups-tlse.fr
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020:02)00535-5

5652
K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
Scheme 1. Synthesis of diimines a±c from benzaldehyde and a,v-diamines.
2. Results and discussion
ane 1 with diimines a±d in anhydrous dichloromethane
occurs instantaneously at room temperature and quantita-
tively gives the corresponding alkyl-bis-:a-aminospiro-
phosphoranes), 2a±d, bearing two Pp±Cp bonds :Scheme 3).
The basic synthetic strategy was ®rst to prepare the diimines
a±d, then to achieve the nucleophilic addition of P-H-spiro-
phosphorane 1 to these diimines according to the Pudovik
reaction, and ®nally to carry out selective hydrolysis of the
alkyl-bis-:P-C-spirophosphoranes) 2 affording bolaform-
and gemini-type surfactants 3 and 4.
As observed for single chain :a-aminoalkyl)spirophosphor-
anes,16c the compounds 2a±d are stable enough in solution
and under argon for NMR characterization, but all attempts
to their puri®cation led to their decomposition into PIV type
compounds. Alkyl-bis-:a-aminospirophosphoranes) 2a±d
have four stereogenic centers: the two pentacoordinated
phosphorus atoms, and the two carbon atoms to wich they
are bonded. These compounds then exist in 16 stereoiso-
meric forms. However, the presence of symmetry elements
in the molecule renders some structures equivalent and
reduces the number of stereoisomers. Thus, we expect
four racemic isomers MRRM/PSSP, MSSM/PRRP, MRRP/
PSSM, and MRSM/PSRP, and two meso forms MRSP and
MSRP. M and P represent, respectively, the left and right
handedness of the pentacoordinated helicoidal spiro-
phosphoranic structure, and R/S the absolute con®gurations
of the P-linked stereogenic carbon centers. Each of these six
diastereoisomers should show in 31P NMR spectra :i) one
signal when the two phosphorus atoms have identical
helicities or they are enantiomers, and :ii) two signals
when the two phosphorus nuclei are magnetically non-
equivalent, leading to eight signals. However, the 31P
NMR spectra analysis consisted of only two high-®eld
signals at about 230 ppm as two doublets with coupling
2.1. Synthesis of diimine linkers
Diimines will be the skeleton of the hydrophobic linkers.
With the aim to prepare bolaforms, three diimines have
been synthetized by condensation of benzaldehyde with
a,v-diamines :¯exible linkers), a,b, and 4,40-ethylene-
dianiline :more rigid linker), c :Scheme 1).
In the case of the diimine d, the semi-rigid and aromatic
spacer for the gemini surfactant, the precursory dialdehyde
D was prepared by O-alkylation of 4-hydroxybenzaldehyde
with a,a0-dichloro-p-xylene, followed by a condensation
reaction with 1-decylamine :Scheme 2).
All these diimines a±d are assumed to exist as anti±anti
compounds since traces of syn isomers have never been
observed by 1H and 13C NMR.
2.2. Addition reaction of P±H bond spirophosphorane
with diimines
2
constants JPH about 16±25 Hz. These two diastereomeric
peaks were separated by about 1 ppm for compounds 2a,b
The addition reaction of two equivalents of spirophosphor-
Scheme 2. Synthesis of dialdehyde D and diimine d.

K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
5653
Scheme 3. Diastereoselective synthesis of the P±C bond alkyl-bis-[:a-aminoalkyl)-spirophosphoranes] 2a±d.
and 2d, and by about 3 ppm in the case of 2c. In each case,
the major isomer corresponded to the more deshielded
signal. This observation may be attributed to the presence
of a long linker, leading to two completly independant P
atoms suf®ciently far from each other so that the molecule
behaves like the monocatenary derivatives. The chemical
shifts of the carbon atoms adjacent to the phosphorus ones
:d 13C ,67) and the corresponding coupling constants
:1JCPˆ190 Hz) clearly demonstrate the replacement of
P±H bonds by new P±C ones and so the presence of
:a-amino)spirophosphorane moieties. The methine proton
resonance appears in most cases as a doublet at approxi-
the P±C bond formation. It is of importance to state that
the introduction of the semi-rigid aromatic linker to the
molecule of bis-imine c decreased the stereoselectivity of
the spirophosphorane addition. This phenomenon can be
attributed to the presence of phenyl groups on nitrogen
atoms of the bis-imine c, decreasing the basicity of the
nitrogen lone pairs and so reducing the rate of formation
of the phosphoranide intermediate and consequently the
addition reaction. The high diastereoselectivity observed
for the other bis-imines :a,b,d) is similar to that of the
monocatenary ones,16c and we can consider that the spacer
is long enough so that the two stereogenic centers were
created independently from each other.
2
mately dˆ4±5 and JHP about 20±25 Hz. The addition
reaction is diastereoselective :75/25#diastereomeric
ratio#95/5) due to the rigid structure of the spirophos-
phoranide intermediate formed by deprotonation of
hydrido-spirophosphorane 1 by the prochiral imines, during
2.3. Selective hydrolysis of alkyl-bis-ꢀa-aminospirophos-
phoranes)
We have already described the selective hydrolysis of the
P-C-spirophosphorane derivatives in the case of single-
chain surfactants.16c The reaction with water led to the
corresponding a-aminophosphonocarboxylic acid monoe-
sters, whereas more drastic acid conditions were required
to obtain free a-aminophosphonic acids. Of course, the
direct conversion of P-C-spirophosphoranes to free phos-
phonic acids was also possible. Thus, bolaform-type 2a±c
and gemini-type 2d bis-spirophosphoranes were hydrolyzed
in situ by water in acetonitrile :1:1 mixture) :Scheme 4).
The reaction occurs instantaneously at room temperature for
compounds 2a,b and 2d, in contrast to 2c which seems to be
more stable. Indeed, its hydrolysis was achieved after 10 h
at room temperature, as monitored by 31P NMR. This can be
due to the presence of aromatic groups as substituent on
amine functions of the molecule, 2c being the only
compound possessing such structure. This stabilization
seems to be very signi®cant because it reduces the rate of
the PvO phosphoryl moiety formation, the main driving
Scheme 4. Synthesis of bolaform- and gemini-type alkyl-bis-[:a-amino-
alkyl)-phosphono-carboxylic acid] surfactants 3a±d.

5654
K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
groups of the monoesters's lateral chain, this non-equiva-
lency being attributed to the proximity of stereogenic
centers.
Obtention of polyfunctional bipolar surfactants 3 bearing
phosphonic acid monoester, a-amino and b-carboxylic
acid groups opens up various application ®elds owing to
their synthetic, chelating and biological properties. Their
usefulness in hydrometallurgy as metal-extractants and
corrosion inhibitors has been described.18 Their metal-ion-
coordinating properties were used in diagnostic medicine as
radioligands for screening experiences, in therapeutic area
as anticancer or anti-viral agents.19 Furthermore, their good
crosslinking ability for cellulose has been shown.20
Treatment of alkyl-bis-[:a-amino)phosphonocarboxylic
acids] 3a,b by 20% aqueous solution of hydrochloric acid
at re¯ux for several hours afforded in nearly quantitative
yields the alkyl-bis-[:a-amino)phosphonic acids] 4a,b by
acidic cleavage of the P±O±C ester moieties :Scheme 5).
Scheme 5. Synthesis of bolaform alkyl-bis-[:a-aminobenzyl)phosphonic
acid] surfactants 4a,b.
force in organophosphorus conversions. The alkyl-bis-
[phosphonocarboxylic acid monoesters] 3a±d have only
two stereogenic centers :the two a-carbon atoms) and
they exist as two diastereomeric products :meso and
racemic forms) giving two distinguishable signals in 31P
NMR spectra. However, the presence of only one signal
31P NMR spectra of the free acids 4a,b exhibit a single
signal :d,10±12) slightly deshielded with respect to the
2
1
corresponding monoesters 3. JHP and JCP coupling
constants, determined from 1H and 13C NMR spectra,
indicate the conservation of P±C bonds under acid con-
ditions. Direct synthesis of bolaforms 4a,b can be achieved
by one-pot hydrolysis of the corresponding bis-spiro-
phosphoranes 2a,b in the presence of 20% hydrochloric
acid under re¯ux for 6 h. On the contrary, when the
gemini-type monoester 3d was treated under the same
conditions, benzylic ether functions of the spacer were
hydrolyzed in addition to carboxyisobutyl moieties,
affording the single-chain :4-hydroxybenzyl):a-amino-
decyl)-phosphonic acid 5 :Scheme 6).
2
as a sharp doublet :with a JPH coupling constant around
16 Hz) in 31P NMR could indicate that the magnetic non-
equivalence of the two phosphorus atoms in the molecule is
too week due to their long hydrophobic spacer: the bipolar
molecule behaves like a single-chain surfactant. The
conversion of the pentacoordinated phosphorus atoms into
tetracoordinated ones was con®rmed by the deshielding of
chemical shifts around dˆ8±17 :i.e. Dd,140 ppm with
respect to chemical shifts of the corresponding P±C bond
spirophosphoranes 2). The chemical shift of a-carbon atoms
1
did not change signi®cantly :d 13C,61) while the JCP
coupling constant decreased by about 45 Hz. As in the
case of single-chain derivatives, the H NMR spectra of
3a±d show two distinguishable singlets for the methyl
This degradation could be surprising because ether cleavage
usually requires more drastic conditions and the use of
concentrated solutions of HI or HBr. However, hydrolysis
1
Scheme 6. Acid hydrolysis of gemini amphiphile 3d into monocatenary :a-aminoalkyl)-phosphonic acid 5.

K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
5655
of alkylarylethers with HBr in phase transfer catalysis
:PTC) conditions or more recently by concentrated aqueous
HCl in the presence of cationic surfactants :micellar
catalysis) has been described.21 In our case, self-assembly
of gemini-type surfactant 3d leading to supramolecular
aggregates :micelles, vesicles, etc) could promote the
hydrolysis of ether moieties.
silica gel :0.063±0.200 mm, Merck) was used. Spiro-
phosphorane 1 was prepared according to the procedure
already described.22
1
In order to readily interpret the H and 13C NMR spectro-
scopical data, the carbon and hydrogen atoms in compounds
D, d, 2d and 3d, bearing a polyaromatic semi-rigid linker,
were numbered as shown below :Scheme 7).
3. Conclusion
4.2. Synthesis
Synthesis of variously substituted bolaform- and gemini-
type alkyl-bis:a-amino-phosphonic acid) surfactants and
their monoesters can be readily performed by diastereo-
selective addition of P±H bond spirophosphoranes to the
corresponding bis-imine precursors, followed by selective
one-pot hydrolysis of the bis-spirophosphorane inter-
mediates containing two Pp±Cp bonds. This procedure,
thanks to its simplicity, should ®nd general application in
the synthesis of various polyfunctional bolaform- and
gemini-type phosphorus amphiphiles. Investigation of the
aggregation behavior of these new surfactants is in progress
and some practical applications including their use as
models of biological membranes, drug transport systems,
extractants or precursors of highly functionalized materials
can be considered.
4.2.1. 1,4-Benzyloxy-bis-ꢀ4-benzaldehyde) ꢀD). Dry potas-
sium carbonate :1.45 g, 10.5 mmol) was added to a solution
of 4-hydroxybenzaldehyde :1.22 g, 10 mmol) in anhydrous
DMF :35 mL) and the heterogeneous mixture was stirred
1 h at 258C. A solution of a-a0-dichloro-p-xylene :0.88 g,
5 mmol) in anhydrous DMF :17 mL) was added dropwise
and the stirring continued for 6 h at 258C. The solid was
separated by centrifugation and the surnageant was evapo-
rated under reduce pressure at 408C. The yellow solid was
dissolved in CH2Cl2 and this organic solution was washed
with water, dried over MgSO4 then evaporated in vacuo to
give a pale yellow solid which was puri®ed by chroma-
tography :silica gel column, eluent: CH2Cl2/EtOH),
:0.69 g, 20%). Mp 160±1628C.23 1H NMR :CDCl3): dˆ
0
9.86 :s, 2H, CHO), 7.82 :m, 4H, HAA ), 7.45 :s, 4H, HC),
7.05 :m, 4H, HXX ), 5.14 :s, 4H, CH2±O). 13C NMR
0
:CDCl3): dˆ190.91 :s, CHO), 163.64 :s, C5), 136.18 :s,
C7), 132.11 :s, C3), 130.22 :s, C2), 127.92 :s, C8), 115.18
:s, C4), 69.92 :CH2±O). IR :KBr, cm21): nˆ1724.6 :CvO).
MS :DCI/NH3): m/z 347 :M11)1, 364 :M1NH4)1.
4. Experimental
4.1. General
NMR spectra were obtained with Brucker AC200 or
250WM spectrometers. IR spectra were recorded on a
Perkin±Elmer FT/IR-1600. Mass spectra were recorded on
a Nermag R10-10H by chemical ionization :DCI/NH3) or by
FAB :positive or negative) modes. Melting points were
measured in open glass capillaries with a Leitz Biomed
apparatus and are uncorrected. Elemental analysis were
performed by the Microanalytical Service Laboratory of
the `Laboratoire de Chimie de Coordination' of Toulouse.
4.3. Diimines derived from benzaldehyde
Benzaldehyde :2.12 g, 20 mmol) was added to a solution of
diamine :10 mmol) in dry chloroform :30 mL). The mixture
Ê
was stirred at 408C for 6 h in the presence of 3 A molecular
sieves. The heterogeneous mixture was centrifuged, the
organic phase was separated, then evaporated to dryness,
and dried under vacuum.
4.3.1.
N,N0-Dibenzylidene-hexane-1,6-diamine
ꢀa).
Benzaldehyde, a,a0-p-dichloroxylene, 1,6-hexanediamine,
1,8-octanediamine, 4,40-ethylene-dianiline, decylamine,
propylene oxide, 2-hydroxyisobutyric acid, phosphorus
trichloride :Aldrich) and 4-hydroxy-benzaldehyde :Acros)
were used as received without further puri®cation. DMF
:Normapur, Prolabo), CHCl3 and CH2Cl2 :Analytical
reagent, SDS), reagent grade products, were maintained
Yellow oil :2.66 g, 91%).24 1H NMR :CDCl3): dˆ8.26 :s,
2H, CHvN), 7.77±7.61 :m, 4H, CHPh), 7.42±7.34 :m, 6H,
3
CHPh), 3.61 :t, JHHˆ6.5 Hz, 4H, CH2±Nv), 1.73 :m, 4H,
CH2±C±N), 1.43 :m, 4H, CH2). 13C NMR :CDCl3): dˆ
160.85 :s, CHvN), 136.39 :s, Cipso), 130.53 :s, CHPh),
128.65 :s, CHPh), 128.10 :s, CHPh), 61.77 :s, CH2±N),
30.94 :s, CH2±C±N), 27.24 :s, CH2). IR :KBr, cm21):
nˆ1644.4 :CvN), 1578.6 :CvC). MS :DCI/NH3): m/z
293 :M11)1.
Ê
over 4 A molecular sieves and stored in dark bottles
protected from moisture. For column chromatography,
4.3.2.
N,N0-Dibenzylidene-octane-1,8-diamine
ꢀb).
Yellow solid :2.72 g, 85%). Mp 35±368C.24 1H NMR
:CDCl3): dˆ8.24 :s, 2H, CHvN), 7.75±7.71 :m, 4H,
3
CHPh), 7.39±7.36 :m, 6H, CHPh), 3.60 :t, JHHˆ7.0 Hz,
4H, CH2±Nv), 1.72 :m, 4H, CH2±C±N), 1.38 :m, 8H,
CH2). 13C NMR :CDCl3): dˆ160.65 :s, CHvN), 136.45
:s, Cipso), 130.45 :s, CHPh), 128.59 :s, CHPh), 128.08 :s,
CHPh), 61.80 :CH2±Nv), 30.99 :s, CH2), 29.47 :s, CH2),
27.39 :s, CH2). IR :KBr, cm21): nˆ1640.9 :CvN), 1570.0
:CvC). MS :DCI/NH3): m/z 321 :M11)1.
1
Scheme 7. Notation used for H and 13C NMR assignments of the carbon
and hydrogen atoms in compounds D, d, 2d and 3d.

5656
K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
4.3.3. N,N0-Dibenzylidene-4,40-ethylenedianiline ꢀc).
Yellow solid :3.53 g, 91%). Mp 167±1698C.25 1H NMR
:CDCl3): dˆ8.48 :s, 2H, CHvN), 7.93±7.48 :m, 10H,
CHPh), 7.22±7.18 :m, 8H, CHC6H4), 2.96 :s, 4H, CH2). 13C
NMR :CDCl3): dˆ159.88 :s, CHvN), 149.96 :s, Cq±N),
139.63 :s, Cq±CH), 136.36 :s, Cq±CH2), 131.33 :s, CHPh),
129.34 :s, CHPh), 128.82 :s, CHPh), 120.97 :s, CHPh), 37.57
:CH2). IR :KBr, cm21): nˆ1619.9 :CvN), 1567.3 :CvC).
MS :DCI/NH3): m/z 389 :M11)1.
4.5.2. Octyl-1,8-bis-[ꢀa-aminobenzyl)spirophosphorane]
2
ꢀ2b). 31P NMR :CDCl3): dˆ231.4 :d, JPHˆ24.7 Hz,
2
1
90%), 232.9 :d, JPHˆ21.2 Hz, 10%). H NMR :CDCl3):
2
dˆ7.35 :m, 10H, CHPh), 4.48 and 4.36 :2d, JHPˆ24.2 Hz,
2
12% and JHPˆ24.9 Hz, 88%, 2H, CH±P), 2.43±2.31 :m,
4H, CH2±N), 1.46 :m, 12H, CH3 endo), 1.41±1.10 :m, 12H,
CH2), 1.05 :m, 12H, CH3 exo). 13C NMR :CDCl3): dˆ172.50
2
2
:d, JCPˆ7.1 Hz, CvO), 135.24 :d, JCPˆ2.6 Hz, Cipso),
2
129.30±127.93 :m, CHPh), 80.95 :d, JCPˆ6.2 Hz,
1
Cq:Me)2), 67.42 :d, JCPˆ190.9 Hz, CH±P), 47.57 :d,
3JCPˆ24.3 Hz, CH2±N), 29.89±26.95 :m, CH2), 26.34 :s,
4.4. Diimine ꢀd) derived from dialdehyde D
3
CH3), 23.47 :d, JCPˆ8.1 Hz, CH3).
The same protocol that for the diimines :a±c) was followed,
using dialdehyde D :1.38 g, 4 mmol) and decylamine
:1.26 g, 8 mmol) in dry chloroform :12 mL).
4.5.3. Bibenzyl-4,40-bis-[ꢀa-aminobenzyl)spirophosphor-
2
ane] ꢀ2c). 31P NMR :CDCl3): dˆ231.6 :d, JPHˆ15.7 Hz,
2
1
75%), 234.5 :d, JPHˆ22.3 Hz, 25%). H NMR :CDCl3):
dˆ7.53±7.39 :m, 10H, CHPh), 6.90±6.61 :m, 8H, CHC6H4),
4.4.1. 1,4-Benzyloxy-bis-N-ꢀ4-benzylidene)-bis-ꢀdecyl-
imine) ꢀd). White solid :1.90 g, 72%). Mp 107±1098C. H
2
2
1
5.40 and 5.36 :2d, JHPˆ22.7 Hz, 25% and JHPˆ16.1 Hz,
75%, 2H, CH±P), 2.66 :s, 4H, CH2), 1.48 :s, 12H, CH3 endo),
0.85 :s, 12H, CH3 exo). 13C NMR :CDCl3): dˆ172.48 :d,
NMR :CDCl3): dˆ8.19 :s, 2H, CHvN), 7.69±7.64 :m, 4H,
0
0
HAA ), 7.45 :s, 4H, HC), 7.01±6.97 :m, 4H, HXX ), 5.11 :s,
2
2JCPˆ5.9 Hz, CvO, main product), 171.75 :d, JCPˆ
3
4H, CH2±O), 3.57 :t, JHHˆ7.0 Hz, 4H, CH2±Nv), 1.67
3
3
7.0 Hz, CvO, minor product), 143.68 :d, JCPˆ10.5 Hz,
:m, 4H, CH2±C±N), 1.26 :m, 28H, CH2), 0.88 :t, JHH
ˆ
3
6.7 Hz, 6H, CH3). 13C NMR :CDCl3): dˆ160.54 :s, C5),
160.00 :s, CHvN), 136.57 :s, C7), 129.68 :s, C2), 129.60
:s, C3), 127.78 :s, C8), 114.89 :s, C4), 69.74 :s, CH2±O),
61.83 :s, CH2±Nv), 31.97±22.76 :m, CH2), 14.21 :s, CH3).
IR :KBr, cm21): nˆ1646.8 :CvN), 1607.2 :CvC). MS
:DCI/NH3): m/z 625 :M11)1, 483 :M2C10H2111)1.
Cq±N, minor product), 143.26 :d, JCPˆ10.8 Hz, Cq±N,
main product), 134.28±133.04 :m, Cq arom), 129.82±
2
114.71 :m, CHarom), 81.48 :d, JCPˆ6.6 Hz, Cq:Me)2,
2
minor product), 81.27 :d, JCPˆ6.5 Hz, Cq:Me)2, main
1
product), 64.91 :d, JCPˆ175.8 Hz, CH±P, minor product),
1
63.71 :d, JCPˆ178.8 Hz, CH±P, main product), 37.18 :s,
CH2), 27.22±23.11 :m, CH3).
4.5. General procedure for the synthesis of alkyl-bis-
[a-aminospirophosphoranes] ꢀ2a±d)
4.5.4. 1,4-Benzyloxy-bis-[ꢀ4-benzyl-a-aminodecyl)spiro-
phosphorane] ꢀ2d). 31P NMR :CDCl3): dˆ231.1 :d,
2
2JPHˆ24.6 Hz, 95%), 232.5 :d, JPHˆ20.3 Hz, 5%). 1H
Diimine a±d :5 mmol) in dry CH2Cl2 :15 mL) was added
dropwise to a stirred solution of spirophosphorane 1 :2.36 g,
10 mmol) in anhydrous CH2Cl2 :15 mL) at room tempera-
ture under argon. The progress of the reaction was followed
by 31P NMR analysis. The addition reaction occured
instantaneously and afforded alkyl-bis-[a-aminospiro-
phosphoranes] 2a±d in quantitative yields. In spite of
their stability in solution under argon during several days,
all attempts to their puri®cation failed due to their decom-
position into tetracoordinated phosphorus compounds. In
order to characterize these alkyl-bis-[a-aminospirophos-
phoranes], the addition reaction was then carried out
directly in a NMR tube :5 mm diameter) in deuterated
solvent under argon, using diimine a±d :0.2 mmol) in
NMR :CDCl3): dˆ7.39 :s, 4H, HC), 7.31±7.25 :m, 4H,
0
HAA ), 6.98±6.93 :m, 4H, HXX ), 5.04 :s, 4H, CH2±O),
0
2
2
4.50 and 4.32 :2d, JHPˆ20.7 Hz, 8% and JHPˆ24.1 Hz,
92%, 2H, CH±P), 2.39 :m, 4H, CH2±N), 1.46 :s, 12H,
CH3 endo), 1.20 :m, 32H, CH2), 1.09 :s, 12H, CH3 exo), 0.85
3
:t, JHHˆ5.1 Hz, CH3). 13C NMR :CDCl3): dˆ172.61 :d,
2JCPˆ6.9 Hz, CvO), 159.03 :s, C5), 136.48 :s, C7),
3
129.95 :d, JCPˆ8.9 Hz, C3), 127.39 :s, C8), 127.34 :s,
2
C2), 115.62 :s, C4), 80.98 :d, JCPˆ6.2 Hz, Cq:Me)2),
1
69.67 :s, C6), 66.75 :d, JCPˆ192.1 Hz, CH±P), 47.55 :d,
3JCPˆ23.8 Hz, CH2±N), 31.91±22.71 :m, CH2), 26.39 :s,
3
CH3), 23.58 :d, JCPˆ7.9 Hz, CH3), 14.19 :s, CH3).
CDCl3 :0.5 mL) and spirophosphorane
1 :94.4 mg,
4.6. General procedure for the synthesis of alkyl-bis-
[carboxyisobutylꢀa-aminoalkyl) phosphonic acid mono-
esters] ꢀ3a±d)
0.4 mmol) in CDCl3 :0.5 mL) at room temperature. The
PV±C-bond bis-spirophosphoranes 2a±d were instan-
taneously and quantitatively formed, then characterized by
1
31P, H and 13C NMR analysis.
Diimine a±d :5 mmol) in anhydrous CH2Cl2 :15 mL) was
added dropwise to a solution of spirophosphorane 1 :2.36 g,
10 mmol) in anhydrous CH2Cl2 :15 mL) under argon at
room temperature. The mixture was stirred for 5±10 min
at room temperature and then concentrated to dryness.
Concerning the compounds 3a,b and 3d, the residue was
treated by CH3CN/H2O 1:1 :50 mL) at room temperature.
The hydrolysis occurred instantaneously and the bolaform
surfactant precipitated. For 3c, the hydrolysis required
longer time :10 h at room temperature) and the use of acetic
acid instead of CH3CN. In all cases, the precipitates were
collected by ®ltration, washed several times with CH3CN,
4.5.1. Hexyl-1,6-bis-[ꢀa-aminobenzyl)spirophosphorane]
ꢀ2a). 31P NMR :CDCl3): dˆ231.5 :d, 2JPHˆ24.7 Hz, 90%),
232.9 :d, 2JPHˆ18.5 Hz, 10%). 1H NMR :CDCl3): dˆ7.26
2
:m, 10H, CHPh), 4.55 and 4.36 :2d, JHPˆ21.4 Hz, 8% and
2JHHˆ24.7 Hz, 9%, 2H, CH±P), 2.30 :m, 4H, CH2±N),
1.44±1.18 :m, 20H, CH2 and CH3 endo), 0.96 :s, 12H,
2
CH3 exo). 13C NMR :CDCl3): dˆ172.28 :d, JCPˆ7.2 Hz,
CvO), 135.15 :s, Cipso), 129.20±128.51 :m, CHPh), 80.82
2
1
:d, JCPˆ5.7 Hz Cq:Me)2), 67.26 :d, JCPˆ191.4 Hz,
3
CH±P), 47.32 :d, JCPˆ24.7 Hz, CH2±N), 29.68 :s, CH2),
26.60 :s, CH2), 26.25 :s, CH3), 23.31 :d, 3JCPˆ8.1 Hz, CH3).

K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
5657
recrystallized from ethanol and then dried under vacuum to
give more or less colored powders.
:CDCl31CD3COOD): dˆ179.01 :s, CvO), 159.21 :s,
C5), 136.52 :s, C7), 130.70 :s, C3), 127.57 :s, C8), 122.04
2
:s, C2), 115.05 :s, C4), 80.14 :d, JCPˆ7.8 Hz, Cq:Me)2),
1
4.6.1. Hexyl-1,6-bis-[carboxyisobutylꢀa-aminobenzyl)-
phosphonic acid monoester] ꢀ3a). White solid :2.55 g,
81%). Mp 201±2038C :from ethanol). 31P NMR :D2O1
69.44 :CH2±O), 60.31 :d, JCPˆ148.5 Hz, CH±P), 46.81
:s, CH2±N), 31.65±22.41 :m, CH2), 27.09 :s, CH3), 25.92
:s, CH3), 13.63 :CH3). IR :KBr, cm21): nˆ3428.6 :OH,
NH), 2522.1 :PO±H), 1723.2 :CvO), 1609.9 :CvC),
1178.0 :PvO), 1070.8 :P±O). MS :Glycerol, FAB.0):
m/z 961 :M11)1, 793 :M2P:O):OH)OC:CH3)2-
COOH11)1. Anal. calcd for C50H78N2O12P2: C, 62.48; H,
8.18; N, 2.91. Found: C, 62.31; H, 7.87; N, 2.75.
2
KOH): dˆ12.9 :d, JPHˆ17.5 Hz). 1H NMR :D2O1
2
KOH): dˆ7.39±7.28 :m, 10H, CHPh), 3.76 :d, JHPˆ
3
18.9 Hz, 2H, CH±P), 2.24 :t, JHHˆ7.4 Hz, 4H, CH2±N),
1.53 :s, 6H, CH3), 1.42 :s, 6H, CH3), 1.29 :m, 4H, CH2±C±
N), 1.05 :m, 4H, CH2). 13C NMR :D2O1KOH): dˆ184.90
3
:d, JCPˆ5.3 Hz, CvO), 136.71 :s, Cipso), 131.70±130.97
2
:m, CHPh), 84.30 :d, JCPˆ9.1 Hz, Cq:CH3)2), 64.30 :d,
4.7. General procedure for the synthesis of alkyl-bis-[a-
aminophosphonic acids] ꢀ4a±b)
3
1JCPˆ146.4 Hz, CH±P), 49.43 :d, JCPˆ10.6 Hz, CH2±N),
3
29.73 :d, JCPˆ3.7 Hz, CH3), 29.35 :d, 3JCPˆ2.3 Hz, CH3),
28.94 :s, CH2), 28.12 :s, CH2). IR :KBr, cm21): nˆ3428.9
:OH, NH), 2531.4 :PO±H), 1724.5 :CvO), 1631.3 :CvC),
1170.1 :PvO), 1067.2 :P±O). MS :Glycerol, FAB.0): m/z
629 :M11)1. Anal. calcd for C28H42N2O10P2: C, 53.50; H,
6.74; N, 4.46. Found: C, 53.11; H, 6.86; N, 4.41.
Their synthesis can be achieved either by acid hydrolysis
of alkyl-bis-[carboxyisobutyl-:a-amino) phosphonic acid
monoesters] 3a,b :Method A), or by one-pot acid hydrolysis
of the reaction mixture :Method B).
Method A. Alkyl-bis-[:a-amino)phosphonocarboxylic acids]
3a,b :2 mmol) in 20% aqueous hydrochloric acid :20 mL)
were re¯uxed for 6 h and the progress of the reaction was
followed by 31P NMR analysis. The mixture was allowed to
cool to room temperature then concentrated to dryness
under vacuum. The crude residue was dissolved in a mini-
mum of absolute ethanol then treated under argon by an
excess of propylene oxide. The precipitate was collected
by ®ltration and puri®ed by H2O/EtOH precipitation, then
dried under vacuum to give a white powder.
4.6.2. Octyl-1,8-bis-[carboxyisobutylꢀa-aminobenzyl)-
phosphonic acid monoester] ꢀ3b). Pale yellow solid
:2.95 g, 90%). Mp 176±1788C :from ethanol). 31P NMR
2
:CD3COOD): dˆ8.6 :d, JPHˆ14.7 Hz). 1H NMR
:CD3COOD): dˆ7.59±7.43 :m, 10H, CHPh), 4.64 :d,
2JHPˆ17.8 Hz, 2H, CH±P), 2.97 :m, 4H, CH2±N), 1.75
:m, 4H, CH2±C±N), 1.63 :s, 6H, CH3), 1.52 :s, 6H, CH3),
1.27 :m, 8H, CH2). 13C NMR :CD3COOD): dˆ184.06 :s,
CvO), 131.12 :s, Cipso), 130.27±129.63 :m, CHPh), 81.46
1
:s, Cq:Me)2), 61.53 :d, JCPˆ147.1 Hz, CH±P), 47.69 :s,
CH2±N), 29.18 :s, CH2), 27.74 :s, CH3), 26.90 :s, CH3),
26.65 :s, CH2), 26.10 :s, CH2). IR :KBr, cm21): nˆ3428.0
:OH, NH), 2545.0 :PO±H), 1726.4 :CvO), 1635.4 :CvC),
1167.9 :PvO), 1067.9 :P±O). MS :Glycerol, FAB.0): m/z
657 :M11)1. Anal. calcd for C30H46N2O10P2: C, 54.87; H,
7.06; N, 4.27. Found: C, 54.20; H, 6.72; N, 4.16.
Method B. The reaction mixture obtained from the addition
reaction of spirophosphorane 1 :0.94 g, 4 mmol) with
diimines a,b :2 mmol) in dry CH2Cl2 :10 mL) under argon
at room temperature was concentrated to dryness under
vacuum after 5±10 min stirring. The crude residue was
treated by 20% aqueous hydrochloric acid :20 mL) under
re¯ux for 6 h. The mixture was then worked up as described
in method A.
4.6.3. Bibenzyl-4,40-bis-[carboxyisobutylꢀa-aminobenzyl)-
phosphonic acid monoester] ꢀ3c). Beige solid :2.35 g,
65%). Mp 170±1728C :from ethanol). 31P NMR :D2O1
When this procedure was applied to compound 3d, the
benzylic ether moieties of the spacer were hydrolyzed in
addition to the ester functions affording the single-chain
derivative 5.
2
KOH): dˆ16.2 :d, JPHˆ22.9 Hz). 1H NMR :D2O1
KOH): dˆ7.40±7.20 :m, 10H, CHPh), 6.77±6.48 :m, 8H,
2
CHC6H4), 4.52 :d, JHPˆ22.9 Hz, 2H, CH±P), 2.42 :s, 4H,
CH2), 1.50 :s, 6H, CH3), 1.47 :s, 6H, CH3). 13C NMR
:D2O1KOH): dˆ175.42 :s, CvO), 148.04 :s, Cq±N),
141.40 :s, Cipso), 135.84 :s, Cq±CH2), 131.87±117.03
4.7.1. Hexyl-1,6-bis-[ꢀa-aminobenzyl)phosphonic acid]
ꢀ4a). White solid :0.41 g, 45%). Mp 238±2418C. 31P
2
2
1
:CHarom), 83.84 :d, JCPˆ9.2 Hz, Cq:Me)2), 60.88 :d,
NMR :D2O): dˆ10.6 :d, JPHˆ15.0 Hz). H NMR :D2O):
3
1JCPˆ141.5 Hz, CH±P), 38.75 :s, CH2), 29.41 :d, JCPˆ
2
dˆ7.32 :m, 10H, CHPh), 4.22 :d, JHPˆ16.0 Hz, 2H, CH±
3.1 Hz, CH3), 29.11 :s, CH3). IR :KBr, cm21): nˆ3407.4
:OH, NH), 2589.9 :PO±H), 1685.6 :CvO), 1616.2 :CvC),
1188.1 :PvO), 1017.6 :P±O). MS :Glycerol, FAB,0): m/z
724 :M21)2.
P), 2.73 :m, 4H, CH2±N), 1.43 :m, 4H, CH2±C±N), 1.03
:m, 4H, CH2). 13C NMR :D2O): dˆ133.05 :d, 2JCPˆ4.3 Hz,
1
Cipso), 131.93±131.30 :m, CHPh), 62.50 :d, JCPˆ138.3 Hz,
3
CH±P), 49.28 :d, JCPˆ5.3 Hz, CH2±N), 27.50 :s, CH2),
27.16 :s, CH2). IR :KBr, cm21): nˆ3377.8 :OH, NH),
4.6.4. 1,4-benzyloxy-4,40-bis-[carboxyisobutylꢀa-amino-
benzyl)phosphonic acid monoester] ꢀ3d). Pale yellow
solid :3.94 g, 82%). Mp 172±1758C :from ethanol). 31P
1607.4 :CvC), 1175.5 :PvO), 1059.2 :P±O). MS
:Glycerol,
FAB.0):
m/z
457
:M11)1,
375
:M2P:O):OH)211)1, 293 :M22[P:O):OH)2]11). Anal.
calcd for C20H30N2O6P2´H2O: C, 50.63; H, 6.80; N, 5.90.
Found: C, 50.61; H, 6.82; N, 5.68.
2
1
NMR :CDCl31CD3COOD): dˆ9.0 :d, JPHˆ17.2 Hz). H
0
:CDCl31CD3COOD): dˆ7.38 :m, 8H, HAA and HC), 6.94
2
0
:m, 4H, HXX ), 5.07 :s, 4H, CH2±O), 4.52 :d, JHPˆ17.9 Hz,
2H, CH±P), 2.83 :m, 4H, CH2±N), 1.64 :m, 4H, CH2±C±
N), 1.59 :s, 6H, CH3), 1.45 :s, 6H, CH3), 1.17 :m, 28H,
4.7.2. Octyl-1,8-bis-[ꢀa-aminobenzyl)phosphonic acid]
ꢀ4b). White solid :0.53 g, 55%). Mp 224±2278C :from etha-
nol). 31P NMR :CD3COOD): dˆ12.4 :d, 2JPHˆ15.8 Hz). 1H
3
CH2), 0.78 :t, JHHˆ6.1 Hz, 6H, CH3). 13C NMR

5658
K. Vercruysse-Moreira et al. / Tetrahedron 58 ꢀ2002) 5651±5658
8. Madelaine-Dupuich, C.; Guidetti, B.; Rico-Lattes, I.; Lattes,
A.; Aubertin, A. M. New J. Chem. 1996, 20, 143±151.
NMR :CD3COOD): dˆ7.74±7.42 :m, 10H, CHPh), 4.64
2
:d, JHPˆ17.2 Hz, 2H, CH±P), 2.94 :m, 4H, CH2±N), 1.79
:m, 4H, CH2±C±N), 1.25 :m, 8H, CH2). 13C NMR
9. :a) Lasic, D. D. La Recherche 1989, 20, 904±915. :b) Suslick,
K. S.; Grinstaff, M. W. J. Am. Chem. Soc. 1990, 112, 7807±
7809. :c) Lawrence, M. J. Chem. Soc. Rev. 1994, 417±424.
10. :a) Dubowchik, G. M.; Firestone, R. A. Tetrahedron Lett.
2
:CD3COOD): dˆ130.64 :d, JCPˆ4.8 Hz, Cipso), 129.99±
1
129.69 :m, CHPh), 61.60 :d, JCPˆ137.9 Hz, CH±P), 47.97
3
:d, JCPˆ7.2 Hz, CH2±N), 29.13 :s, CH2), 26.66 :s, CH2),
26.05 :s, CH2). IR :KBr, cm21): nˆ3748.5 :OH, NH),
1612.8 :CvC), 1175.5 :PvO), 1084.5 :P±O). MS
:Glycerol, FAB.0): m/z 485 :M11)1. Anal. calcd for
C22H34N2O6P2´0.5H2O´0.5HCl: C, 51.64; H, 6.99; N, 5.47.
Found: C, 52.61; H, 7.25; N, 5.57.
È
1996, 37, 6465±6468. :b) Walde, P.; Wessicken, M.; Radler,
U.; Berclaz, N.; Conde-Frieboes, K.; Luisi, P. L. J. Phys.
Chem. B 1997, 101, 7390±7397. :c) Fyles, T. M.; Loock,
D.; Zhou, X. J. Am. Chem. Soc. 1998, 120, 2997±3003 and
references therein.
11. Fornasier, R.; Scrimin, P.; Tecilla, P.; Tonellato, U. J. Am.
Chem. Soc. 1989, 111, 224±229.
4.7.3. Decyl-[a-aminoꢀp-hydroxybenzyl)]phosphonic
acid ꢀ5). Beige solid :0.68 g, 50%). Mp 214±2168C :from
12. Newman, S. P.; Jones, W. New J. Chem. 1998, 105±115.
13. :a) Cristau, H. J.; Mouchet, P.; Dozol, J. F.; Rouquette, H.
Heteroat. Chem. 1995, 6, 533±544. :b) Herlinger, A. W.;
Chiarizia, R.; Ferraro, J. R.; Rickert, P. G.; Horwitz, E. P.
Solvent Extr. Ion Exch. 1997, 15, 401±416.
2
ethanol). 31P NMR :CD3COOD): dˆ13.0 :d, JPHˆ
1
16.2 Hz). H NMR :CD3COOD): dˆ7.40±6.90 :m, 4H,
2
CHarom), 4.49 :d, JHPˆ17.6 Hz, 1H, CH±P), 2.91 :m, 2H,
CH2±N), 1.74 :m, 2H, CH2±C±N), 1.29 :m, 14H, CH2),
3
0.90 :t, JHHˆ5.7 Hz, 3H, CH3). IR :KBr, cm21): nˆ
14. :a) Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1993, 115,
10083±10090. :b) Frindi, M.; Michels, B.; Levy, H.; Zana, R.
Langmuir 1994, 10, 1140±1145. :c) Song, L. D.; Rosen, M. J.
Langmuir 1996, 12, 1149±1153. :d) Bhattacharya, S.; De, S.
Langmuir 1999, 15, 3400±3410.
3351.2 :OH, NH), 1615.2 :CvC), 1164.2 :PvO), 1043.7
:P±O). MS :Glycerol, FAB.0): m/z 344 :M11)1.
15. :a) Pestman, J. M.; Terpstra, K. R.; Stuart, M. C. A.; van
Doren, H. A.; Brisson, A.; Kellogg, R. M.; Engberts,
J . B. F. N.Langmuir 1997, 13, 6857±6860. :b) Sommerdijk,
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