SHORT COMMUNICATION

DOI: 10.1002/ejoc.201500772

Tetrasulfonated 1,2-Bis(diphenylphosphanyl)ethane as a Building Block for the

Synthesis of Disulfonated Alkyldiphenylphosphanes

Julien Denis,[a,b] Michel Ferreira,[a,b] Hervé Bricout,[a,b] Cécile Machut,[a,b]

Sébastien Tilloy,*[a,b] and Eric Monflier[a,b]

Keywords: Biphasic catalysis / Organometallic catalysis / Phosphanes / Sulfonation / Water chemistry

A new and convenient route to various water-soluble alkyldi- phenylphosphane. This methodology allowed the production
phenylphosphanes is proposed starting from tetrasulfonated of disulfonated n-octyl, n-dodecyl, n-hexadecyl, phenethyl,
1,2-bis(diphenylphosphanyl)ethane (DPPETS). DPPETS is and but-3-enyl diphenylphosphanes with satisfactory yields.
alkylated and then cleaved to give the disulfonated alkyldi-

Introduction recting effect of the protonated phosphorus centre in acidic

Water-soluble phosphanes have found numerous applica-
tions in organometallic catalysis as transition-metal ligands,
not only in academic research but also in industrial pro-
cesses.[1–4] In most cases, a water-soluble phosphane is ob-
tained by functionalizing a hydrophobic phosphane with
hydrophilic substituents. The first, and still most commonly
used, water-solubilizing substituent is the sodium sulfonate
group. This sulfonate group is most commonly introduced
to aryl substituents on phosphanes by electrophilic sulfon-
ation by using H2SO4 or SO3/H2SO4 (oleum) followed by
neutralization with aqueous sodium hydroxide. This group
is an attractive water-solubilizing moiety because it is stable
under a variety of reaction conditions. Numerous pathways
are described in the literature for the synthesis of sulfonated
phosphanes.[1] As a particular example, the Scheme 1 repre-
sents the classical synthesis of a disulfonated alkyldiphenyl-
phosphane.
Scheme 1. Classical pathway for sulfonation reaction of an alkyldi-
phenylphosphane.
Sulfonation of phenyl groups linked to the phosphorus
atom exclusively occurs in the meta-position due to the di-
[a] Univ. Artois, UMR 8181, Unité de Catalyse et de Chimie du
Solide (UCCS),
62300 Lens, France
E-mail: sebastien.tilloy@univ-artois.fr
http://www.uccs.univ-artois.fr/sebastientilloy.htm
[b] CNRS, UMR 8181, Unité de Catalyse et de Chimie du Solide
(UCCS),
59000 Lille, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500772.
medium. The protonated phosphorus also deactivates the
phenyl ring regarding the sulfonation, which often results
in the need to use harsh conditions (high temperature, high
oleum amount or long reaction times). These standard
sulfonation conditions are quite severe and if the R group
is oleum-sensitive, this method is unfortunately not conve-
nient. This is the case for the synthesis of disulfonated alkyl-
diphenylphosphane with an R group such as a saturated
linear chain (with R ⬎ C6), a phenylalkyl or an alkenyl
substituent. For alkyldiphenylphosphanes with an alkyl
chain higher than hexyl, our group has clearly shown that
sulfonation of these phosphanes in the presence of oleum
was unsuccessful, due to the cleavage of the alkyl chain dur-
ing the sulfonation process,[5,6] whereas the sulfonation
worked in the case of shorter chains.[7] Concerning the
phenylalkyldiphenylphosphanes, the phenyl attached to the
alkyl chain and the two phenyl groups linked to the phos-
phorus atom are not independent towards the sulfonation
reaction. Indeed, it is impossible, with this method, to selec-
tively produce a disulfonated phenylalkyldiphenylphos-
phane. Finally, the double bond of an alkenyl group would
be protonated under acidic conditions and would lead to
side reactions such as Friedel–Crafts alkylations on the aro-
matic rings. To circumvent these difficulties, an alternative
is to introduce the oleum-sensitive group after the sul-
fonation step. We propose herein a new methodology to ac-
cess disulfonated alkyldiphenylphosphane from tetrasulfon-
ated 1,2-bis(diphenylphosphanyl)ethane (DPPETS)[8,9] and
an alkyl halide. The desired water-soluble phosphanes can
be obtained by alkylation then cleavage of DPPETS. This
strategy uses the capacity of the quaternary bis-phos-
phonium salts of 1,2-bis(diphenylphosphanyl)ethane
(DPPE) to be cleaved by lithium aluminium hydride (Li-
AlH4) producing an alkyldiphenylphosphane with loss of
the carbon bridge between the two phosphorus atoms.[10]

Eur. J. Org. Chem. 2015, 5509–5512 © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 5509
SHORT COMMUNICATION
We report here the synthesis of five new disulfonated alkyl-
diphenylphosphanes (1–5; Scheme 2) by using this new
methodology.
Scheme 2. Synthesized disulfonated alkyldiphenylphosphanes.
Results and Discussion
The general pathway proposed to synthesize these water-
soluble phosphanes is described in Scheme 3. For the alkyl-
ation step, DPPETS was dissolved in N-methyl-2-pyrrol-
idone (NMP) and then alkyl bromide was added. To ensure
a complete alkylation of the two phosphorus atoms, the re-
action mixture was heated at 130 °C whilst stirring for 3
days. Depending on the nature of alkyl group used, either
the bis-phosphonium salt precipitated during the reaction
or addition of diethyl ether was necessary to precipitate it.
In each case, the precipitate was washed with diethyl ether
in a Soxhlet apparatus to eliminate the excess alkyl bromide.
For the cleavage step, the bis-phosphonium salt was intro-
duced into a suspension of LiAlH4 in anhydrous tetra-
hydrofuran (THF) and this mixture was refluxed for 24 h.
The use of LiAlH4 resulted in a reductive cleavage ac-
companied by the loss of ethylene and H2. The mechanism
of the cleavage is described in Scheme 4 by analogy with
the mechanism proposed for DPPE.[10] After the cleavage,
a treatment was necessary to eliminate the excess of LiAlH4
and to recover the water-soluble phosphane. If the nature
of R group allowed it, the phosphorus atom was protected
with BH3 to prevent oxidation during the treatment. The
excess of LiAlH4 was neutralised with an aqueous solution
of sulfuric acid. Inspired by a procedure described in the
Scheme 3. General pathway for the synthesis of the disulfonated alkyldiphenylphosphanes: (i) Alkylation: R-Br/NMP; (ii) Cleavage: 1)
LiAlH4/THF 2) BH3/THF 3) H2SO4/H2O 4) N(n-C8H17)3/CHCl3 5) NaOH/H2O 6) allyl alcohol.
Scheme 4. Cleavage mechanism of the bis-phosphonium salt for the synthesis of the disulfonated alkyldiphenylphosphanes.
5510 www.eurjoc.org © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Denis, M. Ferreira, H. Bricout, C. Machut, S. Tilloy, E. Monflier
literature, the sulfonated phosphanes in their acid form
were mixed with trioctylamine to separate them from the
lithium and aluminium salts.[11,12] The phosphane trioctyl-
ammonium salt was recovered from the acidic aqueous
layer by the addition of chloroform and this organic layer
was washed with water until neutral pH was reached. The
phosphane sodium salt was recovered by a succession of
extractions from the chloroform solution with an aqueous
sodium hydroxide solution. To separate the eventual by-
products, each fraction was analysed by 31P{1H} NMR
spectroscopy and the fractions for which a unique signal
was observed were gathered and concentrated under vac-
uum. If the phosphorus atom was protected with BH3, the
deprotection of the borane/phosphane adduct was achieved
by reaction with allyl alcohol in water at 110 °C for 24 h.
The phosphane was recovered by evaporation of residual
allyl alcohol, alkyl borane and water.
The global yields are 45, 45, 38, 48 and 23 % for phos-
phanes 1, 2, 3, 4 and 5, respectively. The lower yield ob-
tained in the case of 5 was because the phosphorus atom
was not protected during the treatment phase and so there
was increased formation of phosphane oxide. Indeed, in this
case, the protection step by BH3 was impossible because the
carbon–carbon double bond of the but-3-enyl group was
sensitive to the presence of BH3 (boration reaction of the
double bond).
The water solubility, the basicity, the critical micelle con-
centration (CMC) and the surface tension (measured at the
CMC) of these phosphanes are presented in Table 1. The
five phosphanes are soluble in water and the water solubilit-
ies are related to the length and the polarity of the R group.
The basicity of these phosphanes was determined by using
the magnitude of the 1J(77Se,31P) coupling constant in the
corresponding selenides.[13] It was found that the basicity
decreases when the coupling constant increases. Phos-
phanes bearing linear alkyl chains (1, 2 and 3) exhibited
similar 1J(77Se,31P) coupling constants (742–743 Hz). When
compared with 4 and 5, these three phosphanes appeared
to be slightly more basic (lower coupling constants). Lower
CMCs (2 and 0.5 mm) were determined for the phosphanes
bearing the longer alkyl chains, 2 and 3 respectively. For
the three other phosphanes, the CMC values are higher,
Eur. J. Org. Chem. 2015, 5509–5512
Tetrasulfonated 1,2-Bis(diphenylphosphanyl)ethane
situated between 13.5 and 15.5 mm. The values of surface
tension at the CMC are lower for the phosphanes bearing
the linear alkyl chain (1, 2 and 3).
Table 1. Properties of disulfonated alkyldiphenylphosphanes (1–5).
Phosphane Water solubility 1 77
J( Se, 31
P) CMC Surface tension
[g L–1] [Hz] [mm] γCMC [mN m–1]
1 100 743 15.5 40
2 50 742 2.0 39
3 3 742 0.5 41
4 300 746 14.5 50
5 150 746 13.5 58
Conclusions
A new and convenient methodology has been presented
for the synthesis of disulfonated alkyldiphenylphosphanes
bearing an alkyl group sensitive to classical sulfonation con-
ditions. This pathway offers new perspectives for the elabo-
ration of original phosphanes and their applications in
aqueous organometallic catalysis. More specifically, the
phosphanes 1–4 will be good candidates for potential appli-
cations in aqueous micellar catalysis because of their sur-
face active properties. Owing to its carbon–carbon double
bond, phosphane 5 represents an interesting building block
for supported catalysts.
Experimental Section
General: All chemicals were purchased from Strem Chemicals,
Sigma–Aldrich or Fisher Scientific. Tetrahydrofuran (THF) and N-
methyl-2-pyrrolidone (NMP) were used anhydrous and free from
peroxides. Other solvents were used as supplied without further
purification and were degassed by bubbling with nitrogen before
each synthesis. Distilled water was used in all experiments. NMR
spectra were recorded on a Bruker DRX300 spectrometer op-
erating at 300.13 MHz for 1H nuclei, 121.49 MHz for 31P nuclei
and 75.49 MHz for 13C nuclei. [D6]DMSO (99.80 % isotopic purity)
and D2O (99.92 % isotopic purity) were purchased from Euriso-
Top. Signals were recorded in terms of chemical shifts and are ex-
pressed in parts per million (δ), multiplicity, coupling constants (in
Hz, rounded to one decimal place), integration and assignments
in that order. The correct assignments of the chemical shifts were
confirmed when necessary by two-dimensional correlation mea-
surements obtained by 1H–1H COSY, 1H–13C HSQC. Mass spectra
were recorded on a MALDI-TOF/TOF Bruker Daltonics Ultraflex
II in positive reflectron mode with 2,5-DHB as matrix. Elemental
analysis was performed using the Thermo Scientific FlashEA 1112
analyzer. Surface tension measurements were obtained by the pen-
dant drop method. A video-based optical contact angle measuring
system (OCA 15EC, Dataphysics) was used, in which the geometri-
cal profile of a pendant drop is compared with the theoretical drop
profile obtained from the Laplace equation.
General Procedure for the Alkylation of DPPETS: Preparation of
1,2-bis[P-alkyl-P,P-bis(m-sodiosulfonatophenyl)phosphonio]eth-
ane dibromide: DPPETS (1 g) was dissolved in anhydrous NMP
(60 mL) under an N2 atmosphere. Then, alkyl halide (10 equiv.)
was added by cannula. The mixture was heated and stirred for 3 d
at 130 °C. If the salt did not precipitate during the reaction, diethyl
Eur. J. Org. Chem. 2015, 5509–5512 © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ether was added. The recovered solid was washed with diethyl ether
in a Soxhlet apparatus to eliminate the excess alkyl bromide.
General Procedure for the Cleavage of 1,2-Bis[P-alkyl-P,P-bis(m-so-
diosulfonatophenyl)phosphonio]ethane Dibromide: Bis-phosphonium
salt (1 g) previously dried overnight under vacuum was introduced
into a suspension of LiAlH4 (10 equiv.) in anhydrous THF
(20 mL). The mixture was refluxed and stirred for 24 h. Except for
phosphane 5, BH3/THF (5 equiv.) was added at 0 °C to protect
the formed product against oxidation, and the reaction media was
evaporated. The residual solid was dissolved in an aqueous solution
of sulfuric acid (50 mL, 0.2 n), then trioctylamine was added
(4.4 equiv.). The phosphane trioctylammonium salt was extracted
by addition of chloroform (50 mL). The phosphane sodium salt
was recovered by a succession of extractions with 1 n NaOH aque-
ous solution. Each fraction was analysed by 31P{1H} NMR spec-
troscopy, and the fractions were concentrated under vacuum. Fi-
nally, except for phosphane 5, the deprotection was performed in
an aqueous solution of allyl alcohol (6 mL, 5:1) for 24 h at 110 °C.
The phosphane was recovered by evaporation to dryness in vacuo.
P-Octyl-P,P-bis(m-sodiosulfonatophenyl)phosphane (1): Yield 45 %;
white powder; 1H NMR (300.13 MHz, [D6]DMSO): δ = 7.68 (d,
3
JH,H = 7.6 Hz, 2 H), 7.56 (d, 3JH-P = 6.9 Hz, 2 H), 7.31 (m, 4 H),
2.03 (m, 2 H), 1.34 (br., 4 H), 1.21 (br., 8 H), 0.83 (t, 3JH,H =
6.6 Hz, 3 H) ppm. 13C{1H} NMR (75.5 MHz, [D6]DMSO): δ =
148.21 (d, 3JC,P = 6.8 Hz), 138.03 (d, 1JC,P = 15.0 Hz), 132.33 (d,
2
JC,P = 15.0 Hz), 129.45 (d, 2JC,P = 22.5 Hz), 128.15 (d, 3JC,P =
5.3 Hz), 126.02 (s), 31.31 (s), 30.55 (d, 2JC,P = 12.7 Hz), 28.76 (s),
28.71 (s), 26.84 (d, 1JC,P = 12.1 Hz), 25.54 (d, 3JC,P = 16.7 Hz),
22.18 (s), 14.07 (s) ppm. 31P{1H} NMR (121.5 MHz, [D6]DMSO):
δ = –18.59 (s) ppm. MS (MALDI-TOF): m/z = 459.04 [M – 2Na
+ 3H]+, 481.01 [M – Na + 2H]+, 502.98 [M + H]+, 524.98 [M
+ Na]+; elemental analysis: calcd(%) for C20H25Na2O6PS2·2H2O
(538.5): C 44.61, H 5.43; found C 44.43, H 5.41.
P-Dodecyl-P,P-bis(m-sodiosulfonatophenyl)phosphane (2): Yield
45 %; white powder; 1H NMR (300.13 MHz, [D6]DMSO): δ = 7.68
(d, 3JH,H = 7.6 Hz, 2 H), 7.56 (d, 3JH-P = 7.1 Hz, 2 H), 7.31 (m, 4
H), 2.03 (m, 2 H), 1.32 (br., 4 H), 1.21 (br., 16 H), 0.84 (br., 3 H)
ppm. 13C{1H} NMR (75.5 MHz, [D6]DMSO): δ = 148.16 (d, 3JC,P
= 6.5 Hz), 138.15 (d, 1JC,P = 15.2 Hz), 132.49 (d, 2JC,P = 16.4 Hz),
129.54 (d, 2JC,P = 22.7 Hz), 128.25 (d, 3JC,P = 6.3 Hz), 126.10 (s),
31.45 (s), 30.58 (d, 2JC,P = 14.1 Hz), 29.16 (s), 28.90 (s), 26.88 (d,
1
JC,P = 12.4 Hz), 25.61 (d, 3JC,P = 17.7 Hz), 22.25 (s), 14.13 (s)
ppm. 31P{1H} NMR (121.5 MHz, [D6]DMSO): δ = –18.53 (s) ppm.
MS (MALDI-TOF): m/z = 559.53 [M + H]+, 581.07 [M + Na]+;
elemental analysis: calcd(%) for C24H33Na2O6PS2·2H2O (594.6): C
48.48, H 6.27; found C 48.67, H 6.29.
P-Hexadecyl-P,P-bis(m-sodiosulfonatophenyl)phosphane (3): Yield
38 %; white powder; 1H NMR (300.13 MHz, [D6]DMSO): δ = 7.65
(d, 3JH,H = 7.7 Hz, 2 H), 7.53 (d, 3JH-P = 7.4 Hz, 2 H), 7.29 (m, 4
H), 2.00 (m, 2 H), 1.29 (br., 4 H), 1.20 (br., 24 H), 0.82 (t, 3JH,H =
6.1 Hz, 3 H) ppm. 13C{1H} NMR (75.5 MHz, [D6]DMSO): δ =
148.10 (br), 138.05 (d, 1JC,P = 15.3 Hz), 132.34 (d, 2JC,P = 14.0 Hz),
129.45 (d, 2JC,P = 20.4 Hz), 128.15 (br), 126.01 (s), 31.45 (s), 30.56
(br), 29.11 (s), 28.80 (s), 26.92 (br), 25.61 (d, 3JC,P = 14.1 Hz), 22.20
(s), 14.07 (s) ppm. 31P{1H} NMR (121.5 MHz, [D6]DMSO): δ =
–18.53 (s) ppm. MS (MALDI-TOF): m/z = 571.21 [M – 2Na +
3H]+, 593.21 [M – Na + 2H]+, 615.17 [M + H]+, 637.15 [M +
Na]+; elemental analysis: calcd(%) for C28H41Na2O6PS2·2H2O
(650.7): C 51.68, H 6.97; found C 51.47, H 6.94.
P-Phenethyl-P,P-bis(m-sodiosulfonatophenyl)phosphane (4): Yield
48 %; white powder; 1H NMR (300.13 MHz, D2O): δ = 7.84 (d,
3
JH,H = 8.6 Hz, 2 H), 7.74 (d, 3JH-P = 7.4 Hz, 2 H), 7.49 (m, 4 H),
www.eurjoc.org 5511
SHORT COMMUNICATION
7.21 (m, 5 H), 2.73 (m, 2 H), 2.51 (m, 2 H) ppm. 13C{1H} NMR
(75.5 MHz, D2O): δ = 142.11 (d, 3JC,P = 7.0 Hz), 141.33 (d, 3JC,P
= 10.1 Hz), 137.85 (d, 1JC,P = 11.5 Hz), 135.22 (d, 2JC,P = 16.4 Hz),
128.92 (br), 128.74 (d, 2JC,P = 15.5 Hz), 128.14 (s), 128.06 (s),
125.85 (s), 125.59 (s), 30.57 (d, 1JC,P = 14.7 Hz), 27.90 (d, 2JC,P =
8.8 Hz) ppm. 31P{1H} NMR (121.5 MHz, D2O): δ = –18.50 (s)
ppm. MS (MALDI-TOF): m/z = 450.97 [M – 2Na + 3H]+, 472.95
[M – Na + 2H]+, 494.91 [M + H]+, 516.90 [M + Na]+; elemental
analysis: calcd(%) for C20H17Na2O6PS2·2H2O (530.5): C 45.28, H
3.99; found C 45.46, H 4.01.
P-But-3-enyl-P,P-bis(m-sodiosulfonatophenyl)phosphane (5): Yield
23 %; white powder; 1H NMR (300.13 MHz, D2O): δ = 7.92 (d,
3
JH,H = 8.0 Hz, 2 H), 7.80 (d, 3JH-P = 7.0 Hz, 2 H), 7.61 (t, 3JH,H
= 7.3 Hz, 2 H), 7.53 (t, 3JH,H = 3JH-P = 7.5 Hz, 2 H), 5.93 (m, 1
H), 5.05 (m, 2 H), 2.33 (m, 2 H), 2.20 (m, 2 H) ppm. 13C{1H}
NMR (75.5 MHz, D2O): δ = 142.23 (d, 3JC,P = 6.6 Hz), 138.29 (d,
3
JC,P = 12.5 Hz), 138.01 (d, 1JC,P = 11.7 Hz), 135.28 (d, 2JC,P =
16.1 Hz), 128.98 (br), 128.80 (d, 2JC,P = 15.1 Hz), 125.67 (s), 114.66
(s), 28.65 (d, 1JC,P = 14.8 Hz), 25.12 (d, 2JC,P = 7.8 Hz) ppm.
31
P{1H} NMR (121.5 MHz, D2O): δ = –15.94 (s) ppm. MS
(MALDI-TOF): m/z = 400.90 [M – 2Na + 3H]+, 422.90 [M – Na
+ 2H]+, 444.88 [M + H]+, 466.86 [M + Na]+; elemental analysis:
calcd(%) for C16H15Na2O6PS2·2H2O (480.4): C 40.00, H 3.99;
found C 39.84, H 3.97.
Acknowledgments
J. D. is grateful to the Ministère de l’Education Nationale, de l’En-
seignement Supérieur et de la Recherche for the Ph.D. grant.
5512 www.eurjoc.org © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J. Denis, M. Ferreira, H. Bricout, C. Machut, S. Tilloy, E. Monflier
Grégory Crowyn and Dominique Prevost are acknowledged for
NMR analysis and technical assistance, respectively.
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Received: June 11, 2015
Published Online: July 24, 2015
Eur. J. Org. Chem. 2015, 5509–5512