Hydroformylation of higher olefins by rhodium/tris-((1H,1H,2H,2H-perfluorodecyl)phenyl)phosphites complexes in a fluorocarbon/hydrocarbon biphasic medium: Effects of fluorinated groups on the activity and stability of the catalytic system

Article abstract of DOI:10.1016/S0040-4020(02)00211-9

The synthesis of three fluorous triarylphosphites in which an 'insulating' ethylene segment separates the perfluoroalkylgroup from the aryl group is described. The stabilities, solubilities and partition coefficients of these new compounds are reported. The complexes generated in situ from these fluorous triarylphosphites and Rh(acac)(CO)₂ have been tested as catalysts for the hydroformylation of various olefins under fluorous biphasic conditions. The activities and the selectivities were found to vary markedly with the position of the perfluoroalkylgroup on the aromatic ring. The possibility to recover the catalytic system was also investigated from consecutive recycling experiments.

Full text of DOI:10.1016/S0040-4020(02)00211-9

TETRAHEDRON
Pergamon
Tetrahedron 58 12002) 3877±3888
Hydroformylation of higher ole®ns by rhodium/tris-
ꢀꢀ1H,1H,2H,2H-per¯uorodecyl)phenyl)phosphites complexes in a
¯uorocarbon/hydrocarbon biphasic medium: effects of ¯uorinated
groups on the activity and stability of the catalytic system
c
c
d
Thomas Mathivet,a Eric Mon¯ier,b,p Yves Castanet, Andre Mortreux and Jean-Luc Couturier
Â
aRhodia, CRA, 52 rue de la Haie Coq, F-93308 Aubervilliers, France
 Â
Lab. Physico-Chimie Interfaces Appl., Faculte des Sciences J. Perrin, Universite d'Artois, Rue Jean Souvraz,
b
SP 18-62307 Lens Cedex, France
 Â
Laboratoire de Catalyse de Lille associe au CNRS, Universite des Sciences et Technologies de Lille, ENSCL,
c
B.P. 108-59652 Villeneuve d'Ascq, France
dAto®na, CRRA, Rue Henri Moissan, 69310 Pierre Benite, France
Received 5 November 2001; accepted 16 January 2002
AbstractÐThe synthesis of three ¯uorous triarylphosphites in which an `insulating' ethylene segment separates the per¯uoroalkylgroup
from the aryl group is described. The stabilities, solubilities and partition coef®cients of these new compounds are reported. The complexes
generated in situ from these ¯uorous triarylphosphites and Rh1acac)1CO)2 have been tested as catalysts for the hydroformylation of various
ole®ns under ¯uorous biphasic conditions. The activities and the selectivities were found to vary markedly with the position of the
per¯uoroalkylgroup on the aromatic ring. The possibility to recover the catalytic system was also investigated from consecutive recycling
experiments. q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
room temperature and can become homogeneous at higher
temperatures.28±33 Obviously, this behavior allows to
combine the activity of homogeneous catalysts with the
simplicity of product isolation. The hydroformylation of
ole®ns in a ¯uorocarbon phase was ®rst reported by Horvath
and Rabai in 1994.18 The rhodium catalyst was dissolved
in the ¯uorous phase by using a trialkylphosphine
P[CH2CH21CF2)5CF3]3 prepared by hydrophosphinylation
of the corresponding ¯uorinated alkene. The ethylene spacer
was necessary to insulate the phosphorus atom from the
strong electron-withdrawing per¯uoroalkyl group. This
catalyst displays satisfactory activities in a per¯uoromethyl-
cyclohexane/toluene solvent system and the normal to
branched aldehyde ratio 1n/i) was comparable to that
obtained in a conventional solvent with HRh1CO)1PPh3)3
1n/iˆ2.9). In 1998, Horvath and co-workers have reported
a detailed study of the hydroformylation of 1-decene and
ethylene using the same catalytic system under batch and
semi-continuous ¯uorous biphasic conditions.19 In this
study, it was demonstrated that the long-term stability of
the ¯uorous catalyst was greater than that of the Rh/PPh3
catalyst. During nine consecutive reaction/separation
cycles, a total turnover of more than 35,000 was reported
with only a loss of 1.8 ppm of Rh/mol of product. Hydro-
formylation in ¯uorous biphasic condition with ¯uorous
triarylphosphites was ®rst investigated by Hope and
co-workers.20,21 The authors reported the hydroformylation
Hydroformylation of higher ole®ns is an important
industrial process where unselective cobalt-based catalysts
have to be employed because the more reactive and selec-
tive rhodium-based catalysts cannot be separated from the
long chain aldehyde products without decomposition.1±3 To
circumvent this problem, four major strategies have been
developed: 1i) anchoring of rhodium catalysts to resins,
polymeric, dendrimeric or inorganic materials;4±7 1ii) the
use of amphiphilic ligands which allows the extraction of
the rhodium catalyst in another phase at the end of the
reaction;8±10 1iii) the use of supercritical ¯uids as reaction
medium,11±15 and 1iv) the use of two-phase system where
the catalyst is dissolved in a phase which contains neither
the substrate nor the products. In this biphasic approach, the
rhodium catalyst can be dissolved in a molten salt,16,17 in
a ¯uorocarbon phase18±21 or aqueous phase containing
generally a mass transfer promotor.22±27
The ¯uorous biphasic catalysis is a particularly elegant
concept as the two phases are generally well separated at
Keywords: ¯uorocarbons; ¯uorous triarylphosphites; rhodium; hydroformyl-
ation; catalyst recovery.
Corresponding author. Tel.: 133-3-21-791-772; fax: 133-3-21-791-736;
e-mail: mon¯ier@univ-artois.fr
p
0040±4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020102)00211-9

3878
T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
Scheme 1. Synthesis of phosphites A, B and C.
of 1-hexene under 20 atm syngas at 708C using tris14-per-
¯uorohexylphenyl)phosphite as ligand. Interestingly, it was
found that the n/i ratio was higher than that observed with
the Rh/P1OPh)3 catalyst and that the catalytic system was
also active for the hydroformylation of internal alkenes.34
the attachment of two per¯uoroalkyl groups per aromatic
ring was also investigated.
As shown in Scheme 1, the route developed for the synthesis
of ¯uorinated analogues of P1OPh)3 is based on a copper-
catalyzed coupling of the Grignard reagents from bromo-
anisoles with 1H,1H,2H,2H-per¯uorodecanyl iodide,
followed by cleavage of methoxy group by BBr3 and
reaction of the corresponding phenol with phosphorus
trichloride.
We report herein our efforts to develop a hydroformylation
process of higher ole®ns in the presence of ¯uorous-soluble
triarylphosphites modi®ed rhodium catalysts.35 We will
describe in a ®rst time the synthesis, the stability, the
solubility and the partition coef®cient of ¯uorous triphenyl-
phosphites in which an insulating ethylene segment sepa-
rates the per¯uoroalkylgroup from the phenyl group and, in
a second time, the activity, selectivity and stability of
catalysts generated in situ from these phosphites and
Rh1acac)1CO)2.
Using this route, tris12-11H,1H,2H,2H-per¯uorodecyl)-
phenyl)phosphite 1A) and tris14-11H,1H,2H,2H-per¯uoro-
decyl)phenyl) phosphite 1B) were easily obtained on multi-
grams scales with overall isolated yields of 35±45%. The
synthesis of a phosphite bearing two per¯uoroalkyl groups
per aromatic ring was more tedious 1overall isolated yield
of 3%). Indeed, the coupling of 2,4-dibromoanisole with
1H,1H,2H,2H-per¯uorodecanyl iodide provided a complex
mixture consisting of 4-bromo-2-11H,1H,2H,2H-per¯uoro-
decyl)anisole 17%), 2-bromo-4-11H,1H,2H,2H-per¯uoro-
decyl)anisole 130%), dimerized and unreacted 1H,1H,2H,
2H-per¯uorodecanyl iodide and unidenti®ed products.
Despite longer reaction times, higher temperatures and
amounts of iodide derivatives have been used, all attempts
to obtain directly in one step the 2,4-di11H,1H,2H,2H-per-
¯uorodecyl)anisole from 2,4-dibromoanisole have failed.
However, we found that the coupling of pure isolated
2. Results
2.1. Synthesis of new ¯uorinated analogues of PꢀOPh)3
In order to minimize the effect of per¯uoroalkyl group, we
decided to synthesize ¯uorous analogues of P1OPh)3 where
aromatic rings are insulated of the per¯uoroalkyl groups by
two methylene groups. Indeed, is was clearly demonstrated
that the insertion of a spacer group between phosphorus
atom and per¯uoroalkyl group reduces greatly the
electron-withdrawing effect of ¯uorous ponytails.19,36±38
For instance, Hope and co-workers have reported that
tris14-11H,1H,2H,2H-¯uorooctyl)phenyl)phosphine and tris-
14-hexylphenyl)phosphine have similar s donor/p acceptor
properties, suggesting that two-methylene groups are
enough to lower the electron-withdrawing effect of ¯uorous
ponytails in the case of ¯uorinated analogues of triphenyl-
phosphine.14 In order to obtain higher ¯uorous solubilities,
2-bromo-4-11H,1H,2H,2H-per¯uorodecyl)anisole with
a
new charge of 1H,1H,2H,2H-per¯uorodecanyl iodide can
afford the target 2,4-di11H,1H,2H,2H-per¯uorodecyl)-
anisole in 11% yield. Cleavage of the methoxy group of
this compound could be easily achieved with BBr3 in
1,1,2-trichlorotri¯uoroethane 185% yield) and reaction
of the corresponding phenol with phosphorus tri-
chloride in an ether/1H-per¯uorooctane mixture gave

T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
3879
Figure 1. Miscibility diagrams of 1-decene/C8F17H and n-undecanal/C8F17H.
tris12,4-bis11H,1H,2H,2H-per¯uorodecyl)phenyl)phosphite
1C) in 93% yield.
data on their relative solubilities were also sought. Thus,
partition coef®cients in a 1-decene/C8F17H mixture were
determined by GC at room temperature. Phosphites A, B,
and C gave a 5/95, 5/95 and 1/99 distribution in a 1-decene/
C8F17H mixture. As expected, these compounds are largely
more soluble in the ¯uorous phase than in organic phase.
However, the partition coef®cients of phosphites A and B
are too low to be considered as totally `immobilized'
ligands. Indeed, they should slowly leach during consecu-
tive reaction/separation cycles. The partition coef®cient
of phosphite C is more suitable for a ¯uorous biphasis
catalysis.
2.2. Stability, solubility and partition coef®cient of
phosphites A, B and C
Phosphites A, B and C proved to be air stable and appeared
less sensitive to hydrolysis than the per¯uoroalkylated
triphenylphosphites that we have previously synthe-
sized.39,40 For example, when phosphite A or B was
dissolved in a water±tetrahydrofuran mixture 150/50; v/v)
under nitrogen, no appreciable hydrolysis was observed
within 48 h. Under the same conditions, the hydrolysis of
tris14-1per¯uorooctyl)phenyl)phosphite 1D) or 2-1per¯uoro-
octyl)phenylphosphite into H3PO3 and the corresponding
phenol derivative was complete after 24 h. The higher
hydrolytic stability of the P±O bond of phosphites A, B or
C compared to per¯uoroalkylated triphenylphosphites can
probably be attributed to the lower electronic in¯uence of
the per¯uoroalkyl solubilizers. In line with this hypothesis,
we found that the IR nCvO value is signi®cantly lower for
complex HRh1CO)1B)3 than that HRh1CO)1D)3 12036 vs
2066 cm21). Surprisingly, the 31P{1H} NMR signals for
complexes HRh1CO)1B)3 and HRh1CO)1P1OC6H5)3 were
different: d 142.68 and 140.98 ppm, respectively. Further-
more, the IR spectrum of HRh1CO)1B)3 showed an IR nCvO
value higher than that of HRh1CO)1P1OC6H5)3 12036 vs
2010 cm21). These data suggest strongly that the ethylene
spacer does not completely insulate the ¯uorinated alkyl
chain from the aromatic ring in terms of electronic
properties.
2.3. Hydroformylation of heavy ole®ns
2.3.1. Mutual miscibility of heavy ole®ns and aldehydes
with ¯uorous solvents. Ef®cient ¯uorous biphasic hydro-
formylation process requires low mutual miscibility of the
reaction products 1aldehydes) and the ¯uorous phase in
order to avoid the loss of the expensive per¯uorous
compounds and catalyst. Thus, accurate knowledge of the
phase equilibrium relationships between the different
components of the system is needed for the design of the
process.
For the ®rst time, n-undecanal, 1-decene and 1H-per¯uoro-
octane were chosen as model components of the hydro-
formylation process. Fig. 1 depicted the variation of the
complete solubility temperature as a function of the compo-
sition of pairs undecanal/C8F17H and 1-decene/C8F17H. As
expected, the chemical nature of the components, the
composition of the mixture and the temperature have a
great in¯uence on the miscibility. For example a solution
of C8F17H saturated with 1-decene contains 5 wt% of
decene at 468C and 10 wt% at 608C. Interestingly, the
heavier and more polar aldehyde is more ef®ciently expelled
from the ¯uorous phase than the parent ole®n. Indeed,
saturation of a solution of C8F17H by undecanal is reached
with only 0.5 and 1 wt% at 46 and 758C, respectively.
Conversely, the solubility of C8F17H in 1-decene and in
undecanal is roughly the same at ambient temperature and
Phosphines A, B and C are, at room temperature, highly
soluble in commercially available solvents namely:
per¯uoroperhydrophenanthrene 1PFPP), per¯uoromethyl-
decalin 1PFMD), per¯uoromethylcyclohexane 1PFMC)
and per¯uorooctyl bromide 1PFOB) and in 1H-per¯uoro-
octane; slightly soluble in tetrahydrofuran and ether; very
slightly soluble in chloroform, toluene, and insoluble in
dimethylsulfoxide and higher hydrocarbons such as
n-decane, n-undecane and n-pentadecane. Quantitative

3880
T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
Table 1. Upper critical solution temperature of different ole®ns and
aldehyde in C8F17H
decalin 1PFMD), per¯uoromethylcyclohexane 1PFMC),
per¯uorooctyl bromide 1PFOB) and 1H-per¯uorooctane
11H-PFO).
Ole®na
Temperature 18C)
Aldehydeb
Temperature 18C)
1-Hexene
1-Octene
1-Decene
1-Dodecene
,20
47
81
.100
n-Heptanal
n-Nonanal
n-Undecanal
n-Tridecanal
37
84
.120
@120
The shapes of the curves of temperature solubility as func-
tion of composition are similar to the one obtained with
C8F17H. All of them exhibit a maximum for about
75±80 wt% of the ¯uorous component. Moreover, except
that of PFOB, the miscibility decreases and thus the upper
critical solution temperature increases upon increasing
the number of carbon atoms of the ¯uorous compound.
Interestingly, at ambient temperature, the quantity of
¯uorous compound in the saturated organic phase is much
lower with PFPP 15 wt%) and PFMD 18 wt%) than with
C8F17H. On the other hand at 808C 1usual reaction tempera-
ture of hydroformylation) the pair PFPP/1-decene and
PFMD/1-decene are only partially miscible with a low
content of the ole®n in the ¯uorous phase. Surprisingly,
substitution of the H atom of C8F17H by bromine in PFOB
has the effect to largely shift down the curve of solubility
and the two phases domain dramatically decreases. Thus,
PFOB does not appear as a good solvent for ¯uorous
biphasic hydroformylation of higher ole®ns.
a
Weight% of ole®n in the mixture at maximum of the solubility curves:
1-hexene: 20%; 1-octene: 25%; 1-decene: 30% and 1-dodecene: 33%.
Weight% of aldehyde in the mixture: 30%.
b
is much higher 110 wt%) than the one of the latter in C8F17H.
However at higher temperature a solution of undecanal
saturated with C8F17H contains a much lower quantity of
C8F17H than the one of 1-decene. Thus the pair undecanal/
C8F17H exhibits an `upper critical solution temperature'
1above which phase separation cannot occur) much higher
1.1208C) than the one of the pair 1-decene-/C8F17H 1808C).
The miscibility of 1H-per¯uorooctane with other higher
ole®ns and the corresponding aldehydes resulting from
their hydroformylation, was also studied. A similar behavior
was observed in each case i.e. the aldehyde and the ¯uorous
compound are always less soluble than the couple ole®n±
C8F17H. It appears also that the solubility is largely
in¯uenced by the size of the organic species. For example,
Table 1 shows that 1-hexene is miscible with C8F17H in all
proportions at ambient temperature whereas the upper
critical solution temperature of the pair 1-dodecene±
C8F17H is above 1008C. Ole®ns smaller than 1-octene
seem pour candidate for ¯uorous biphasic hydroformyl-
ation.
2.3.2. Hydroformylation of 1-decene. The phosphites A, B
and C were tested in ¯uorous biphasic hydroformylation of
1-decene under standard reaction conditions 1808C, 40 bar
CO/H2 1/1) with Rh1acac)1CO)2 as catalyst precursor and a
phosphite/Rh ratio of 5 1see Scheme 2). Different ¯uorous
solvents were used in the absence of any other organic
solvent or in the presence of toluene.
The progress of the reaction was monitored by GC and the
results obtained are listed in Table 2. In the absence of
organic solvent 1pure 1-decene) and with C8F17H as ¯uorous
solvent, all phosphites induced high catalytic activities
1entries 1±3). Nevertheless the bulky ortho substituted
phosphites A and C differ from the para substituted B
Finally, the in¯uence of the nature of the per¯uorous solvent
was also investigated. Fig. 2shows the miscibility diagrams
of 1-decene with various per¯uorous solvents such as
per¯uoroperhydrophenanthrene 1PFPP), per¯uoromethyl-
by much higher activities 1TOF.10,000 vs 3900 h21
,
Figure 2. Miscibility diagrams of 1-decene with various ¯uorous solvents. PFPP: per¯uoroperhydrophenanthrene; PFMD: per¯uoromethyldecalin; PFMC:
per¯uoromethylcyclohexane, PFOB: per¯uorooctyl bromide, 1H-PFO: 1H-per¯uorooctane.

T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
3881
Scheme 2. Hydroformylation of 1-decene in ¯uorous biphasic medium using phosphites A, B and C as ligand.
Table 2. Hydroformylation of 1-decene under ¯uorous biphasic conditions
Entry
Phosphite
Per¯uorous solvent
Organic solvent
ta 1min)
TOFb 1h21
)
n/ic
Aldehyde selectivityc 1mol%)
1
2
3
4
5
6
7
A
B
C
B
B
B
B
C8F17H
8FCH
None
15
30
121100.00
60
60
90
90
10000
3900
2
3500
3800
2500
2300
2.0
3.5
85
3.0
3.0
3.3
3.6
85
95
C8F17H
C8F17H
Toluene
C8F17H
C8F17H
C8F17H
17
C8F17H
C8F17H
PFMC
PFMD
PFPP
98
98
95
95
Experimental conditions: 1-decene: 10.86 g 177.4 mmol); Rh1acac)1CO)2: 10 mg 10.039 mmol, ole®n/Rhˆ2000); phosphite: 0.194 mmol 1P/Rhˆ5); ¯uorous
solvent: entries 1±3: 15 ml, entries 4±7: 10 ml; toluene: 10 ml; n-undecane 1internal standard for GC analysis): 1.21 g; T: 808C; P: 40 bar CO/H2 11/1).
Time required to reach 100% conversion.
a
b
TOF: turn over frequencies de®ned as the number of moles of substrate transformed per hour and per moles of catalyst calculated from the slope at tˆ0 of the
curve conversionˆf1t).
c
n/i and aldehyde selectivity calculated at 70% conversion. The ratio of the products that are formed 1both aldehydes and internal decenes) is constant at the
beginning of the reaction. On the other hand when the reaction of 1-decene begins to slow down, the internal decenes previously formed are hydroformylated
resulting in the production of several branched aldehydes. Thus to compare the results properly we decided to present in the table the data obtained at the
same conversion 170%).
respectively), by lower normal to iso ratio of aldehydes
1n/iˆ2.0 with A or C and 3.5 with B) and a lower aldehyde
selectivity 185% vs 95%). Addition of an organic co-solvent
1toluene) led to little changes in the results. The reaction
proceeded with slightly lower activity and n/i ratio and a
slightly higher aldehyde selectivity 1compare entries 2and
4). In the same way, the substitution of C8F17H by other
¯uorous compounds had practically no effect on the n/i
ratio and the aldehyde selectivity. On the other hand, the
nature of the ¯uorous phase had a great in¯uence on the
activity since the TOF dropped from 3800 h21 with PFMC
to 2500 and 2300 h21 with PFMD and PFPP, respectively.
larly as 1-decene giving a n/i ratio of 3.0 and an aldehyde
selectivity of 95 mol% but the activity markedly drops with
1-dodecene.
As expected the reactivity falls again with internal ole®ns.
Indeed the activity observed with 2-octene is three fold
smaller than the one of 1-octene under the same conditions
and the activity is again divided by a factor two when going
from 2-octene to 4-octene. The aldehyde distribution is also
markedly different with 2-octene and 4-octene. In the case
of 2-octene, 2-methyloctanal and 2-ethylheptanal resulting
directly from the hydroformylation of the substrate without
isomerization, are the main reaction products 190 mol%).
On the other hand with 4-octene isomerization markedly
occurs particularly at the beginning of the reaction 1about
50 mol% of isomerization at 20 min) and leads to a large
extent of 2-methyloctanal and 2-ethylheptanal.
2.3.3. Hydroformylation of various internal or terminal
ole®ns under ¯uorous biphasic conditions. In order to
determine the scope and limitation of the process, the hydro-
formylation of various heavy linear ole®ns and cyclohexene
has been studied with phosphite B as ligand and C8F17H as
¯uorous phase.
Finally, cyclic alkenes such as cyclohexene are practically
inactive under these reaction conditions since its conversion
reaches only 25 mol% after 6 h.
From Table 3, it appears that terminal ole®ns behave simi-
Table 3. Hydroformylation of various higher ole®ns under ¯uorous biphasic conditions
Entry
Ole®n
t 1min)a
TOFb 1h21
)
n/i
3.0
3.0
Aldehyde selectivityc 1mol%)
1
21-Decene
3
4
5
6
1-Octene
60
3600
3.0
2600
1200
440
45
95
60
3500
98
1-Dodecene
2-Octene
4-Octene
60
90
150
94
82
77
100
d
±
±
e
Cyclohexene
±
Experimental conditions: ole®n: 77.4 mmol; Rh1acac)1CO)2: 10 mg 10.039 mmol, ole®n/Rhˆ2000); phosphite B: 0.194 mmol 1P/Rhˆ5); C8F17H: 10 ml,
toluene: 10 ml, n-undecane 1internal standard for GC analysis):1.21 g; T: 808C; P: 40 bar CO/H2 11/1).
Time required to reach 100% conversion.
a
b
De®ned as in Table 2.
Calculated at 70% conversion as in Table 2.
c
d
Aldehyde distribution 1mol%): n-nonanal: 5%; 2-methyloctanal: 60%; 2-ethylheptanal: 30%; 2-propylhexanal: 5%.
Aldehyde distribution 1mol%): n-nonanal: 8%; 2-methyloctanal: 28%; 2-ethylheptanal: 26%; 2-propylhexanal: 38%.
e

3882
T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
Figure 3. Conversion of 1-decene during recycle experiments with phos-
phites A, B and C. Experimental condition: Rh1acac)1CO)2: 0.038 mmol,
phosphite: 0.193 mmol; 1H-per¯uorooctane: 15 ml; 1-decene: 77.4 mmol;
undecane: 7.74 mmol 1GC internal standard); T: 808C. P: 40 atm of CO/H2
11/1); Reaction time: 10 min.
Figure 5. Hydroformylation of 1-deceneÐvariation of the aldehyde selec-
tivity during recycle experiments with phosphites A, B and C. Experimental
condition: Rh1acac)1CO)2: 0.038 mmol, phosphite: 0.193 mmol; 1H-
per¯uorooctane: 15 ml; 1-decene: 77.4 mmol; undecane: 7.74 mmol 1GC
internal standard); T: 808C. P: 40 atm of CO/H2 11/1); Reaction time:
10 min.
2.3.4. Catalyst recovery and reuse. 1-Decene and C8F17H
have been chosen as model to investigate the recovery and
reuse of the catalytic system with phosphites A±C. The
reaction was conducted as described above except that the
duration of each test was ®xed to 10 min in order to avoid
the leveling of performances that could occur when total
conversion is reached. As illustrated in Fig. 3, the activity
was maintained during the three ®rst cycles with phosphites
A and C and even slightly increased in the case of B. On the
other hand, the conversion dramatically dropped during the
course of the fourth cycle with phosphite A. Moreover, in
this last case, whereas in the ®rst recycles the organic phases
were colorless, the yellow color at the end of the last test
revealed an important leaching of the Rh from the ¯uorous
to the organic phase.
3. Discussion
The results obtained with phosphites A and C differ from
whose of B by a remarkably higher initial rate of hydro-
formylation of 1-decene. Concomitantly they lead to more
modest n/i ratio and aldehyde selectivity. This difference is
probably due to the fact that with the bulky orthosubstituted
phosphite A and C only one phosphite coordinates to the Rh
center in competition with CO to give the active species
HRhL1CO)3 1LˆA or C).41±42 In contrast with phosphite
B, as in classical triphenyl phosphine modi®ed catalyst,
two phosphites bond to the rhodium. This assertion is in
agreement with the fact that the catalyst precursor
Rh1acac)1CO)2 reacts with these phosphites in the absence
of syn gas, to give Rh1acac)1CO)L 1LˆA or C) with phos-
phites A or C whereas Rh1acac)L2 1LˆB) is obtained with
B. The complex HRhL1CO)3 has, similar to HRh1CO)4, a
strong aptitude to CO dissociation compared with HRh-
1CO)L2. With only one phosphite bonded to Rh the complex
easily binds to the ole®n initiating a very fast reaction cycle.
Due to the large space available in comparison with the
HRh1CO)2L2 system and the easy CO dissociation the
reaction giving the branched aldehyde as well the b-H
elimination proceed with relative ease resulting in a modest
linearity and aldehyde selectivity.
Finally, Figs. 4 and 5 show that the n/i ratio and the alde-
hyde selectivity regularly decreased after each cycle and the
effect of the recycle on the n/i ratio was more marked in the
case of phosphite B.
It is also noteworthy that, even if B leads to a lower activity
in hydroformylation of 1-decene in C8F17H than A and C
this activity is similar to the one observed with P1OPh)3 in
homogeneous medium and under the same reaction con-
ditions. On the other hand, the activity markedly drops
when PFMD or PFPP are used instead of C8F17H as ¯uorous
solvents. In the same way, whereas 1-octene and 1-decene
are hydroformylated with about the same activity, this one
is much lower with 1-dodecene. These observations are
probably in connection with the fact that at the reaction
temperature 1808C), as above mentioned, the miscibility of
PFMD or PFPP with 1-decene 1see Fig. 2) as well as the
one of 1-dodecene with C8F17H 1see Table 1) are not
total. Consequently, the reaction occurs in these cases in
Figure 4. Hydroformylation of 1-deceneÐvariation of the n/i ratio during
recycle experiments with phosphites A, B and C. Experimental condition:
Rh1acac)1CO)2: 0.038 mmol, phosphite: 0.193 mmol; 1H-per¯uorooctane:
15 ml; 1-decene: 77.4 mmol; undecane: 7.74 mmol 1GC internal standard);
T: 808C. P: 40 atm of CO/H2 11/1); Reaction time: 10 min.

T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
3883
Scheme 3. Proposed mechanism for the reaction of phosphites with aldehydes.
three-phase-system 1two liquid phases and a gas phase) and
the concentration of the ole®n in the ¯uorous phase that
contains the catalyst is much lower than in the case of a
two-phase system 1a liquid phase and a gas phase). As the
order with respect of the substrate in the hydroformylation
reaction of heavy ole®ns is positive at low ole®n concen-
tration,42±43 the decrease in concentration of the ole®n in the
catalytic phase induces a decrease in the rate of the reaction.
ing that the decay of phosphites A±C is not due to their
per¯uorous group. On the other hand, the steric hindrance
due to the ¯uorous ponytail in the case of A and C has the
effect to reduce their reactivity that explains their better
stability. The fact that, at 808C under the reaction con-
ditions, undecanal is slightly soluble in C8F17H 1see Fig.
1) is also a favorable factor that should limit the decompo-
sition of the different phosphites dissolved in C8F17H.
However, the solubility is still obviously too high to prevent
the reaction between undecanal and the phosphites A±C.
From this, it may be deduced that the use of an organic
¯uorous biphasic system induces little change in the hydro-
formylation reaction in comparison with the classical
homogeneous system as long as the reaction medium
becomes homogeneous at the reaction temperature and
provided that the ¯uorous pony tail of the ligand does not
lead to a modi®cation of the catalytic species.
Thus, the decrease in the n/i ratio as well as the decrease in
the aldehyde selectivity and the increase in the activity
during the different recycles, are probably ascribable to
the decrease in the ligand/Rh ratio due to the leaching of
the phosphites and to the decomposition of phosphites. In
connection with that, it is noteworthy that the effect on the
n/i ratio and on the activity are more marked with phosphite
B which is the less stable.
From a recycling viewpoint, it appears that the catalytic
system obtained with phosphites B and C possesses in
contrast with the one resulting of phosphite A, a good
reuse ®tness since the activity remained constant or slightly
increased after the different recycles. However the decrease
in the n/i ratio and in the aldehyde selectivity after each
cycle 1even with phosphites B and C) indicate that a
modi®cation of the catalytic system occurs during each
reuse presumably by a decrease in the P/Rh ratio. This
decrease could be due in the case of A and B to a leaching
of the phosphite 1A and B have a modest partition coef-
®cient) and/or to a decay of the phosphite. Actually, the
attack of triphenylphosphites by aldehydes in organic
medium is a known reaction which proceeds via the
formation of dioxophospholanes that evolve to give a
phosphite oxide and an epoxide 1see Scheme 3).44±47
From the coloration of the organic phase with phosphite A at
the end of the last recycles, it is obvious that there is an
important leaching of the rhodium during these tests in
contrast with phosphites B or C. However, the partition
coef®cient of A is not lower than the one of B and phosphite
A has a better stability. To explain this apparent contradic-
tion, it should be noticed that the main catalytic species are
different with phosphite A and C, on the one hand, and B on
the other hand 1HRh1CO)3L and HRh1CO)2L2, respectively;
LˆA, B or C). Complex HRh1CO)31A) with only three
per¯uorous groups per Rh is probably less ¯uorophilic
than HRh1CO)31C) or HRh1CO)21B)2 which have six
per¯uorous groups per Rh. Thus HRh1CO)31A) is less
retained in the ¯uorous phase than its counterparts particu-
larly when the ratio P/Rh begins to decrease due to the
decomposition and/or the leaching of the ligand.
In order to con®rm this hypothesis, we sought to determine
the stability of the different phosphites A, B and C under the
reaction conditions. A sample of each phosphite was heated
at 808C in mixtures of C8F17H/1-decene 11/1, v/v) or
C8F17H/1-decene/undecanal 11/1/1, v/v/v). In the absence
of undecanal all the phosphites remained unchanged after
1 h. In contrast, with undecanal, 50% of B was converted
into oxidation products. Ortho substituted phosphite A and
C appeared more stable but during the same time 20%
decomposition again occurred. Blank experiment conducted
with P1OPh)3 under the same conditions 1C8F17H/1-decene/
undecanal mixture) led to 40% of decomposition, suggest-
4. Conclusion
Although the rhodium complexes associated with phos-
phites A, B and C can catalyze the hydroformylation of
higher ole®ns in a ¯uorocarbon/hydrocarbon biphasic
medium, this work demonstrates that `simple' ¯uorinated
analogues of P1OPh)3 are not stable in the hydroformylation
conditions. The synthesis of more stable ¯uorous-soluble

3884
T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
triarylphosphites and the use of phosphite C in others tran-
sition metal catalyzed reactions are currently under way in
our laboratories.
matrix. Gas chromatography was performed on Chrompack
CP-9001 gas chromatograph equipped with a CPSil-5CB
column 125 m£0.32mm) and FID detector. Nirogen was
the carrier gas and the temperature program was from 80
to 2008C at a heating rate of 58C/min.
5. Experimental
5.1. General
5.4. Synthesis of phosphites and precursors
5.4.1. 2-ꢀ1H,1H,2H,2H-Per¯uorodecyl)anisole. To a sus-
pension of magnesium 10.44 g, 18.06 mmol, 1.0 equiv.) in
25 ml of THF was introduced the 2-bromoanisole 19.03
mmol, 0.5 equiv.). After few min, the reaction began and
9.03 mmol of the 2-bromoanisole 10.5 equiv.) in THF
110 ml) was added dropwise. The reaction mixture was
vigorously stirred at room temperature for 1 h. The reaction
mixture was then ®ltered and added dropwise at 08C over
1 h to a stirred suspension of 1H,1H,2H,2H-per¯uoro-
decanyl iodide 118.06 mmol, 1.0 equiv.) and CuI 11.8
mmol, 0.1 equiv.) in 20 ml of anhydrous THF. The mixture
was slowly warmed to room temperature and stirred for
24 h. Then, hydrochloric acid solution 160 ml, 2N) and
ether 150 ml) were added. After 15 min, the two phases
were separated and the aqueous phase was extracted with
ether 13£30 ml). The combined organic layers were washed
with 10% Na2S2O3 solution 1100 ml), dried over anhydrous
Na2SO4 and ®ltered. The solvent was removed on a rotary
evaporator and the resulting residue was puri®ed by column
chromatography on silica gel 1PE until elution of unreacted
1H,1H,2H,2H-per¯uorodecanyl iodide, then PE/CH2Cl2
180/20); v/v). Yield: 4.50 g 145%) of a colorless oil
All synthesis and catalytic reactions were performed under
nitrogen using standard Schlenk techniques. All solvents
and liquid reagents were degassed by bubbling nitrogen
for 15 min before each use or by two freeze-pump-thaw
cycles before use.
5.2. Solvents and materials
Solvents were employed as follows: THF distilled from
sodium/benzophenone; Et2O: distilled from sodium/potas-
sium; toluene, distilled from sodium; NEt3, CH2Cl2, distilled
from CaH2. Petroleum ether 1PE, bp 60±808C) was distilled
before use. Dicarbonylacetylacetonato rhodium1I), 2,4-bro-
moanisole, copper1I) iodide, magnesium turnings, phos-
phorus trichloride and 4-octene were purchased from
Aldrich Chemicals in their highest purity and used without
further puri®cation. Per¯uoromethylcyclohexane was
obtained from Aldrich Chemicals and distilled from
CaH2. Cyclohexene, 1-hexene, 1-octene, 2-octene, 4-octene,
1-decene, 1-dodecene, 4-bromoanisole, 2-bromoanisole and
BBr3 were purchased from Acros Chemicals and used as
received. 1H,1H,2H,2H-per¯uorodecyl iodide was gener-
ously supplied by Ato®na and was used as received.
1H-per¯uorooctane, per¯uorooctyl bromide and 1,1,2-tri-
chlorotri¯uoroethane were generously supplied by Ato®na
and were distilled from CaH2. Per¯uoromethyldecaline and
per¯uoroperhydrophenanthrene were supplied by Fluoro-
chem and distilled from CaH2. Carbon monoxide/hydrogen
mixture 11/1) was used directly from cylinders 1.99.9%
pure; Air Liquide). Tris14-1per¯uorooctyl)phenyl)phosphite
was prepared according to published procedures.39
1
1Rfˆ0.73; PE/CH2Cl2 190/10) v/v); NMR H 1CDCl3) d
1ppm): 7.23 1td, 1H, Jˆ7.8 and 1.6 Hz, 5-ArH), 7.15 1dd,
1H, Jˆ7.4 and 1.6 Hz, 3-ArH), 6.91 1td, 1H, Jˆ7.4 and
1.0 Hz, 4-ArH), 6.87 1d, 1H, Jˆ7.8 Hz, 6-ArH), 3.84 1s,
3
3H, ±OCH3), 2.90 1m, 2H, JHHˆ8.2Hz, ±C H2±CH2±
3
3
C8F17), 2.35 1m, 2H, JHFˆ18.6 Hz, JHHˆ8.2Hz, ±CH 2±
CH2±C8F17); NMR 19F{1H} 1CDCl3) d 1ppm): 281.04 1t,
3
3
3F, JFFˆ9.7 Hz, ±CF3), 2115.04 1t, 2F, JFFˆ11.8 Hz,
CF2± in a of ±CH2±), 2121.98 1m, 2F, ±CF2±), 2122.15
1m, 4F, 2£±CF2±), 2122.97 1m, 2F, ±CF2±), 2123.76 1m,
2F, ±CF2±), 2126.36 1m, 2F, ±CF2±); NMR 13C{1H}
1CDCl3) d 1ppm): 157.61 1s, 1-C arom), 130.08 1s, 3-CH
arom), 128.19 1s, 5-CH arom), 127.69 1s, 2-C arom), 120.73
1s, 4-CH arom), 110.45 1s, 6-CH arom), 55.23 1s, ±OCH3),
5.3. Product analysis
1
All H, 13C, 19F and 31P NMR spectra were recorded at
2
ambient probe temperature at 300.13, 75.5, 282.4 and
121.49 MHz on Bruker Avance DRX, respectively.
Chemical shifts 1d) are given in ppm and are referenced
to internal tetramethylsilane 11H and 13C NMR), external
CFCl3 119F NMR) and external 85% H3PO4 131P NMR).
Abbreviations for NMR spectral multiplicities are as
follows: brˆbroad, sˆsinglet, dˆdoublet, tˆtriplet,
ttˆtriplet of triplets, ddˆdoublet of doublets, tdˆtriplet of
doublets, mˆmultiplet. The coupling constants 1J) are in
Hertz. Infrared spectra were obtained from NaCl plates or
Nujol mulls using a Nicolet 510 FTIR spectrophotometer
and wavelengths 1n) are reported in cm21. Abbreviations for
IRFT spectra are as follows: wˆweak, mˆmedium,
sˆstrong, vs: very strong. Microanalyses were conducted
by Wolff laboratories 1Clichy, France). The EI mass spectra
were recorded on a Nermag R10-10B mass spectrometer.
The MALDI-TOF mass spectra were performed on a
Finnigan MAT VISION 2000 spectrometer using 3,5-di-
hydroxybenzoic acid or 2,3,4-trihydroxyacetophenone as
31.14 1t, JCFˆ21.8 Hz, ±CH2±CH2±C8F17), 21.94 1t,
3JCFˆ4.3 Hz, ±CH2±CH2±C8F17), 105±120 1complex
signals of ±CF2± and ±CF3); MS 1EI) m/z: 554 1M1,
67.7), 535 1M12F, 8.9), 515 1M122F2H, 2.2), 135
1M12C8F17, 2.0), 121 1M12CH2C8F17, 100), 91
1[C5H32C2H4]1, 32.3), 69 1CF31, 8.9); IRFT 1KBr) n
1cm21): 3073 1w), 3009 1w), 2953 1w), 2843 1w), 1605
1w), 15921w), 1497 1s), 1469 1m), 1441 1w), 1370 1w),
1331 1w), 1287 1m), 1244 1vs), 1206 1vs), 1150 1vs), 1114
1m), 1083 1m), 1051 1m), 1033 1w), 9721w), 7521m), 704
1w), 656 1w).
5.4.2. 4-ꢀ1H,1H,2H,2H-Per¯uorodecyl)anisole. The titled
compound was prepared in a fashion similar to 2-11H,1H,
2H,2H-per¯uorodecyl)anisole from 4-bromoanisole 19.03
mmol). After addition of Grignard reagent to suspension
of 1H,1H,2H,2H-per¯uorodecanyl iodide and CuI, the
mixture was stirred at room temperature for 4 h instead of
24 h. After an identical workup, chromatography yielded

T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
3885
1
6.52g 165%) of a white solid mp: 35 8C 1Rfˆ0.67; PE/
1[C5H32C2H4]1, 2.3), 77 1[C5H32CH2]1, 1.3), 69 1CF3
,
1.5); IRFT 1KBr) n 1cm21): 3013 1w), 2952 1w), 2918 1w),
2878 1w), 2845 1w), 1615 1w), 1506 1s), 1494 1s), 1469 1m),
1457 1w), 1370 1m), 1330 1m), 1242 1vs), 1205 1vs), 1150
1vs), 1113 1s), 1088 1s), 1034 1m), 975 1w), 808 1w), 705
1m), 656 1m).
1
CH2Cl2 180/20) v/v); NMR H 1CDCl3) d 1ppm): 7.13 1m,
2H, Jˆ8.6 and 2.5 Hz, 3.5-ArH), 6.86 1m, 2H, Jˆ8.6 and
2.5 Hz, 2.6-ArH), 3.79 1s, 3H, ±OCH3), 2.86 1m, 2H,
3
3JHHˆ8.4 Hz, ±CH2±CH2±C8F17), 2.33 1m, 2H, JHFˆ
3
18.3 Hz, JHHˆ8.4 Hz, ±CH2±CH2±C8F17); NMR 19F{1H}
3
1CDCl3) d 1ppm): 281.13 1t, 3F, JFFˆ9.5 Hz, ±CF3),
3
2114.99 1t, 2F, JFFˆ12.9 Hz, ±CF2± in a of ±CH2±),
5.4.4. 2-ꢀ1H,1H,2H,2H-Per¯uorodecyl)phenol. A solution
of BBr3 111.73 mmol, 1.3 equiv.) in anhydrous toluene
110 ml) was added dropwise at room temperature over
15 min to a stirred solution of 2-11H,1H,2H,2H-per¯uoro-
decyl)anisole 19.02mmol, 1.0 equiv.) in anhydrous toluene
140 ml). The reaction mixture was vigorously stirred under
N2 ¯ow at room temperature for 24 h. Then, the reaction
mixture was poured into a mixture of water 150 ml) and
ether 130 ml). The two phases were separated and the
aqueous phase was extracted with ether 13£30 ml). The
combined organic layers were washed with water
12£50 ml), dried over anhydrous Na2SO4 and ®ltered.
The solvent was removed on a rotary evaporator and the
resulting residue was puri®ed by column chromatography
on silica gel 1CH2Cl2). Yield: 3.946 g 181%) of a white solid
2122.02 1m, 2F, ±CF2±), 2122.24 1m, 4F, 2£±CF2±),
2123.04 1m, 2F, ±CF2±), 2123.82 1m, 2F, ±CF2±),
2126.45 1m, 2F, ±CF2±); NMR 13C{1H} 1CDCl3) d
1ppm): 154.321s, 1-C arom), 131.51 1s, 4-C arom), 129.57
1s, 3,5-CH arom), 114.30 1s, 2,6-CH arom), 55.21 1s,
2
±OCH3), 33.41 1t, JCFˆ22.0 Hz, ±CH2±CH2±C8F17),
3
25.69 1t, JCFˆ3.9 Hz, ±CH2±CH2±C8F17); 105±120
1complex signals of ±CF2± and ±CF3); MS 1EI) m/z: 554
1M1, 17.3), 535 1M12F, 6.3), 134 1M12H2C8F17, 1.6),
121 1M12CH2C8F17, 100), 91 1[C5H32C2H4]1, 1.9), 77
1[C5H32CH2]1, 1.3), 69 1CF31, 2.0); IRFT 1KBr) n
1cm21): 3024 1w), 2967 1w), 2840 1w), 1613 1w), 1585
1w), 1516 1s), 1454 1w), 1374 1w), 1336 1m), 1287 1m),
1245 1s), 1202 1s), 1146 1s), 1115 1m), 1102 1m), 1075
1w), 1026 1m), 986 1w), 961 1w), 8321w), 8121w), 714
1w), 659 1m). Anal. Calcd for C17H11F17O: C, 36.85; H,
1.98; found: C, 38.11; H, 2.14.
1
mp: 678C 1Rfˆ0.74; CH2Cl2); NMR H 1CDCl3) d 1ppm):
7.14 1d, 1H, Jˆ7.7 Hz, 3-ArH), 7.121td, 1H, Jˆ7.7 and
1.7 Hz, 5-ArH), 6.89 1td, 1H, Jˆ7.7 and 1.0 Hz, 4-ArH),
6.73 1d, 1H, Jˆ7.7 Hz, 6-ArH), 4.75 1s, 1H, ±OH), 2.92
3
5.4.3. 2,4-Bisꢀ1H,1H,2H,2H-per¯uorodecyl)anisole. The
titled compound was synthesized in two steps. The ®rst
step was similar to that described for 4-11H,1H,2H,2H-
per¯uorodecyl)anisole except than 2,4-dibromoanisole was
used as starting material. After an identical workup,
chromatography on silica gel 1PE/CH2Cl2 180/20) v/v)
yielded 1.03 g 19%) of 4-bromo-2-11H,1H,2H,2H-per¯uoro-
decyl)anisole as a colorless oil 1Rfˆ0.85) and 3.431 g 130%)
of 2-bromo-4-11H,1H,2H,2H-per¯uorodecyl)anisole as a
white solid 1Rfˆ0.59). The second step was analogous to
that reported for 4-11H,1H,2H,2H-per¯uorodecyl)anisole
except than 2-bromo-4-11H,1H,2H,2H-per¯uorodecyl)-
anisole that was isolated in the ®rst step was the starting
material. The crude product was puri®ed by column
chromatography to afford 2,4-bis11H, 1H,2H,2H-per¯uoro-
decyl)anisole as a colorless oil. Yield: 1.95 g 111%) 1Rfˆ
1m, 2H, JHHˆ8.3 Hz, ±CH2±CH2±C8F17), 2.40 12m,
3
H,3JHFˆ18.9 Hz, JHHˆ8.3 Hz, ±CH2±CH2±C8F17); NMR
3
19F{1H} 1CDCl3) d 1ppm): 281.021t, 3F, JFFˆ9.9 Hz,
3
±CF3), 2115.14 1t, 2F, JFFˆ12.2 Hz, ±CF2± in a of
±CH2±), 2121.98 1m, 2F, ±CF2±), 2122.19 1m, 4F, 2£
±CF2±), 2122.98 1m, 2F, ±CF2±), 2123.79 1m, 2F,
±CF2±), 2126.38 1m, 2F, ±CF2±); NMR 13C{1H}
1CDCl3) d 1ppm): 153.56 1s, 1-C arom), 130.61 1s, 3-CH
arom), 128.19 1s, 5-CH arom), 125.89 1s, 2-C arom), 121.35
2
1s, 4-CH arom), 115.40 1s, 6-CH arom), 31.021t, JCFˆ
3
21.8 Hz, ±CH2±CH2±C8F17), 21.65 1t, JCFˆ4.1 Hz,
±CH2±CH2±C8F17); 105±120 1complex signals of ±CF2±
and ±CF3); MS 1IE) m/z: 540 1M1, 49.0%), 521 1M12F,
6.1%), 501 1M122F2H, 2.9%), 121 1M12C8F17, 2.2%),
120 1M12H2C8F17, 2.6%), 107 1M12CH2C8F17, 100%),
91 1[C5H32C2H4]1, 3.0%), 77 1[C5H32CH2]1, 7.5%), 69
1CF31, 7.2%); IRFT 1KBr) n 1cm21): 3504 1s), 34021s),
3044 1w), 2996 1w), 2948 1w), 1595 1m), 1509 1m), 1460
1m), 1373 1m), 1356 1m), 1336 1s), 1242 1vs), 1218 1vs),
1205 1vs), 1148 1vs), 1116 1s), 1078 1m), 1043 1w), 1025
1w), 9721w), 954 1w), 765 1m), 746 1m), 655 1m).
1
0.75; PE/CH2Cl2 190/10) v/v); NMR H 1CDCl3) d 1ppm):
7.06 1dd, 1H, Jˆ8.3 and 2.2 Hz, 5-ArH), 6.99 1d, 1H,
Jˆ2.2 Hz, 3-ArH), 6.80 1d, 1H, Jˆ8.3 Hz, 6-ArH), 3.82
3
1s, 3H, ±OCH3), 2.86 1m, 4H, JHHˆ8.6 Hz, ±CH2±CH2±
3
3
C8F17), 2.33 1m, 4H, JHFˆ18.6 Hz, JHHˆ8.6 Hz, ±CH2±
CH2±C8F17); NMR 19F{1H} 1CDCl3) d 1ppm): 281.09 1t,
6F, 3JFFˆ9.3 Hz, 2£±CF3), 2115.08 1m, 4F, 2£±CF2± in a
of ±CH2±), 2122.03 1m, 4F, 2£±CF2±), 2122.24 1m, 8F,
4£±CF2±), 2123.04 1m, 4F, 2£±CF2±), 2123.80 1m, 4F,
2£±CF2±), 2126.44 1m, 4F, 2£±CF2±); NMR 13C{1H}
1CDCl3) d 1ppm): 156.45 1s, 1-C arom), 131.35 1s, 4-C
arom), 130.13 1s, 3-CH arom), 128.12 1s, 2-C arom),
127.79 1s, 5-CH arom), 110.70 1s, 6-CH arom), 55.34 1s,
±OCH3), 33.39 1t, 2JCFˆ22.0 Hz, ±CH2±CH2±C8F17 in b of
4-C arom), 31.11 1t, 2JCFˆ21.8 Hz, ±CH2±CH2±C8F17 in b
of 2-C arom), 25.66 1br s, ±CH2±CH2±C8F17 in a of 4-C
5.4.5. 4-ꢀ1H,1H,2H,2H-Per¯uorodecyl)phenol. The titled
compound was prepared in a fashion similar to 2-11H,
1H,2H,2H-per¯uorodecyl)phenol from 4-11H,1H,2H,2H-
per¯uorodecyl)anisole 19.02mmol). The reaction mixture
was vigorously stirred under N2 ¯ow at room temperature
for 4 h instead of 24 h. Yield: 4.286 g 188%) of a white solid
1
mp: 888C 1Rfˆ0.48; CH2Cl2); NMR H 1CDCl3) d 1ppm):
7.08 1m, 2H, Jˆ8.5 and 2.5 Hz, 3,5-ArH), 6.78 1m, 2H,
Jˆ8.5 and 2.5 Hz, 2,6-ArH), 4.75 1s, 1H, ±OH), 2.84 1m,
3
3
2H, JHHˆ8.4 Hz, ±CH2±CH2±C8F17), 2.32 1tt, 2H, JHFˆ
3
3
arom), 22.02 1t, JCFˆ4.3 Hz, ±CH2±CH2±C8F17 in a of
18.3 Hz, JHHˆ8.4 Hz, ±CH2±CH2±C8F17); NMR 19F{1H}
3
2-C arom), 105±120 1complex signals of ±CF2± and
±CF3); MS 1EI) m/z: 1000 1M1, 0.3), 981 1M12F, 0.1),
581 1M12C8F17, 0.5), 567 1M12CH2C8F17, 100), 162
1M122C8F17, 8.8), 148 1M122CH2C8F17, 8.1), 91
1CDCl3) d 1ppm): 281.08 1t, 3F, JFFˆ9.7 Hz, ±CF3),
3
2114.93 1t, 2F, JFFˆ12.5 Hz, ±CF2± in a of ±CH2±),
2121.99 1m, 2F, ±CF2±), 2122.21 1m, 4F, 2£±CF2±),
2123.00 1m, 2F, ±CF2±), 2123.78 1m, 2F, ±CF2±),

3886
T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
2126.41 1m, 2F, ±CF2±); NMR 13C{1H} 1CDCl3) d 1ppm):
154.321s, 1-C arom), 131.51 1s, 4-C arom), 192.57 1s,
toluene 150 ml) and dissolved in THF 130 ml). Triethyl-
amine 11.0 ml, 7.23 mmol, 4.0 equiv.) was added to this
solution. Phosphorus trichloride 10.2ml, 2.42mmol,
1.3 equiv.) dissolved in 15 ml of THF was added dropwise
at 08C for 1.5 h under N2 to the stirred solution of 2-11H, 1H,
2H, 2H-per¯uorodecyl)phenol. Subsequently the reaction
mixture was stirred for 4 h at room temperature. The
amine salts formed were removed by ®ltration over dried
silica gel under N2 with further 40 ml of THF. The solvent
was removed in vacuo to afford the pure phosphite 1A).
Yield: 2.95 g 197%) of a white solid mp: 688C NMR
2
3,5-CH arom), 115.69 1s, 2,6-CH arom), 33.31 1t, JCFˆ
3
21.8 Hz, ±CH2±CH2±C8F17), 25.67 1t, JCFˆ3.9 Hz,
±CH2±CH2±C8F17); 105±120 1complex signals of ±CF2±
and ±CF3); MS 1IE) m/z: 540 1M1, 4.7), 521 1M12F, 2.5),
120 1M12H±C8F17, 3.1), 107 1M12CH2C8F17, 100), 91
1[C5H32C2H4]1, 0.8), 77 1[C5H32CH2]1, 0.8%), 69
1CF31, 0.5) Anal. Calcd for C16H9F17O: C, 35.58; H, 1.66;
found: C, 36.63; H, 1.80; IRFT 1KBr) n 1cm21): 3274 1w),
3026 1w), 2949 1w), 2876 1w), 1615 1m), 1602 1m), 1517
1vs), 1458 1m), 1373 1m), 1336 1m), 1294 1m), 1239 1vs),
1217 1vs), 1202 1vs), 1147 1vs), 1116 1m), 1080 1m), 1032
1w), 973 1w), 958 1m), 822 1m), 719 1m), 705 1m), 657 1m).
1
31P{1H} 1CDCl3) d 1ppm): 1132.71 1s); NMR H 1CDCl3)
d 1ppm): 7.22 1br d, 3H, Jˆ8.0 Hz, 3£3-ArH), 7.18 1m, 6H,
3£4 and 5-ArH), 7.09 1m, 3H, Jˆ8.0 Hz, 3£6-ArH), 2.85
3
1m, 6H, JHHˆ8.2Hz, 3 £±CH2±CH2±C8F17), 2.26 1tt, 6H,
3
5.4.6. 2,4-Bisꢀ1H,1H,2H,2H-per¯uorodecyl)phenol.
A
3JHFˆ18.4 Hz, JHHˆ8.2Hz, 3 £±CH2±CH2±C8F17); NMR
3
solution of BBr3 11.35 mmol, 1.3 equiv.) in toluene 14 ml)
was added dropwise at room temperature over 15 min to a
stirred solution of 2,4-bis11H,1H,2H,2H-per¯uorodecyl)-
anisole 11.036 g, 1.04 mmol, 1.0 equiv.) in CF2ClCCl2F
110 ml). The reaction mixture was vigorously stirred under
N2 ¯ow at room temperature for 24 h. Then, the reaction
mixture was poured into a mixture of water 130 ml) and
ether 130 ml). The two phases were separated and the
aqueous phase was extracted with ether 13£30 ml). The
combined organic layers were washed with water
12£50 ml), dried over anhydrous Na2SO4 and ®ltered. The
solvent was removed on a rotary evaporator and the
resulting residue was puri®ed by column chromatography
on silica gel 1CH2Cl2). Yield: 0.869 g 185%) of a white solid
19F{1H} 1CDCl3) d 1ppm): 281.39 1t, 9F, JFFˆ9.8 Hz, 3£
±CF3), 2115.49 1m, 6F, 3£±CF2± in a of ±CH2±),
2122.28 1m, 6F, 3£±CF2±), 2122.49 1m, 12F, 6£±CF2±),
2123.29 1m, 6F, 3£±CF2±), 2123.97 1m, 6F, 3£±CF2±),
2126.71 1m, 6F, 3£±CF2±); NMR 13C{1H} 1CDCl3) d
2
1ppm): 149.93 1d, JCPˆ3.0 Hz, 1-C arom), 130.79 1s,
3
3-CH arom), 130.60 1d, JCPˆ1.9 Hz, 2-C arom), 128.27
3
1s, 5-CH arom), 124.79 1s, 4-CH arom), 119.86 1d, JCPˆ
13.3 Hz, 6-CH arom), 31.15 1t, 2JCFˆ22.0 Hz, ±CH2±CH2±
3
C8F17), 21.57 1t, JCFˆ3.8 Hz, ±CH2±CH2±C8F17), 105±
120 1complex signals of ±CF2± and ±CF3); MS 1MALDI)
m/z: 1648 1M1); IRFT 1KBr) n 1cm21): 1490 1m), 1458 1w),
1373 1w), 1332 1w), 1244 1vs), 1221 1vs), 1202 1vs), 1176
1s), 1150 1vs), 1135 1s), 1116 1m), 1080 1m), 1039 1w), 1026
1w), 973 1w), 889 1m), 819 1w), 770 1w), 656 1m).
1
mp: 638C 1Rfˆ0.75; CH2Cl2); NMR H 1CDCl3) d 1ppm):
6.98 1d, 1H, Jˆ2.2 Hz, 3-ArH), 6.95 1dd, 1H, Jˆ8.0 and
2.2 Hz, 5-ArH), 6.68 1d, 1H, Jˆ8.0 Hz, 6-ArH), 4.73 1s, 1H,
5.4.8. Trisꢀ4-ꢀ1H,1H,2H,2H-per¯uorodecyl)phenyl)phos-
phite ꢀB). The titled compound was prepared in a fashion
similar to tris12-11H,1H,2H,2H-per¯uorodecyl)phenyl)-
phosphite from 4-11H,1H,2H,2H-per¯uorodecyl)phenol.
Yield: 2.969 g 197%) of a white solid mp: 838C NMR
3
±OH), 2.90 1m, 2H, JHHˆ8.2Hz, ±C H2±CH2±C8F17 in a
3
of 2-C arom), 2.83 1m, 2H, JHHˆ8.2Hz, ±C H2±CH2±
3
C8F17 in a of 4-C arom), 2.34 1m, 4H, JHFˆ19.7 Hz,
3JHHˆ8.2Hz, 2 £±CH2±CH2±C8F17); NMR 19F{1H}
3
1
1CDCl3) d 1ppm): 281.04 1t, 6F, JFFˆ9.6 Hz, 2£±CF3),
31P{1H} 1CDCl3) d 1ppm): 1127.95 1s); NMR H 1CDCl3)
3
2114.91 1t, 2F, JFFˆ11.4 Hz, ±CF2± in g of 4-C arom),
d 1ppm): 7.16 1m, 6H, Jˆ8.7 and 2.5 Hz, 3£3,5-ArH), 7.10
3
2115.08 1t, 2F, JFFˆ12.2 Hz, ±CF2± in g of 2-C arom),
1m, 6H, Jˆ8.7 Hz, 3£2,6-ArH), 2.89 1m, 6H, 3JHHˆ8.4 Hz,
3
3
2121.98 1m, 4F, 2£±CF2±), 2122.20 1m, 8F, 4£±CF2±),
2122.99 1m, 4F, 2£±CF2±), 2123.78 1m, 4F, 2£±CF2±),
2126.39 1m, 4F, 2£±CF2±); NMR 13C{1H} 1CDCl3) d
1ppm): 152.28 1s, 1-C arom), 131.95 1s, 4-C arom), 130.54
1s, 3-CH arom), 127.84 1s, 5-CH arom), 126.20 1s, 2-C
3£±CH2±CH2±C8F17), 2.34 1tt, 6H, JHFˆ18.1 Hz, JHH
ˆ
8.4 Hz, 3£±CH2±CH2±C8F17); NMR 19F{1H} 1CDCl3) d
3
1ppm): 281.61 1t, 9F, JFFˆ9.7 Hz, 3£±CF3), 2115.19 1t,
6F, 3JFFˆ12.8 Hz, 3£±CF2± in a of ±CH2±), 2122.24 1m,
6F, 3£±CF2±), 2122.49 1m, 12F, 6£±CF2±), 2123.32 1m,
6F, 3£±CF2±), 2124.02 1m, 6F, 3£±CF2±), 2126.82 1m,
6F, 3£±CF2±); NMR 13C{1H} 1CDCl3) d 1ppm): 150.46 1d,
2JCPˆ2.9 Hz, 1-C arom), 135.35 1s, 4-C arom), 129.69 1s,
2
arom), 115.65 1s, 6-CH arom), 33.321t, JCFˆ21.6 Hz,
2
±CH2±CH2±C8F17 in b of 4-C arom), 30.96 1t, JCFˆ
22.5 Hz, ±CH2±CH2±C8F17 in b of 2-C arom), 25.67 1t,
3JCFˆ3.6 Hz, ±CH2±CH2±C8F17 in a of 4-C arom), 21.75
1t, 3JCFˆ3.9 Hz, ±CH2±CH2±C8F17 in a of 2-C arom), 105±
120 1complex signals of ±CF2± and ±CF3); MS 1EI) m/z:
986 1M1, 16.2), 967 1M12F, 6.9), 567 1M12C8F17, 11.0),
553 1M12CH2C8F17, 100), 134 1M122C8F17, 3.2), 120
1M122CH2C8F17, 21.1), 91 1[C5H32C2H4]1, 3.3), 77
1[C5H32CH2]1, 1.9), 69 1CF31, 2.5); IRFT 1KBr) n
1cm21): 3489 1m), 3431 1m), 2958 1w), 2876 1w), 1509
1m), 1457 1w), 1373 1m), 1335 1s), 1236 1vs), 1202 1vs),
1149 1vs), 1115 1s), 1079 1m), 980 1w), 968 1w), 704 1w),
658 1m).
3
3,5-CH arom), 121.16 1d, JCPˆ6.7 Hz, 2,6-CH arom),
2
33.16 1t, JCFˆ22.0 Hz, ±CH2±CH2±C8F17), 25.92 1s,
±CH2±CH2±C8F17), 105±120 1complex signals of ±CF2±
and ±CF3); MS 1MALDI) m/z: 1648 1M1). Anal. Calcd for
C48H24F51O3P: C, 34.98; H, 1.45; found: C, 35.67; H, 1.60;
IRFT 1KBr) n 1cm21): 1506 1m), 13721w), 1334 1w), 1236
1s), 1204 1vs), 1149 1vs), 1114 1m), 1082 1w), 871 1w), 657
1w).
5.4.9. Trisꢀ2,4-bisꢀ1H,1H,2H,2H-per¯uorodecyl)phenyl)-
phosphite ꢀC). The 2,4-bis11H,1H,2H,2H-per¯uorodecyl)-
phenol 10.87 mmol, 3.0 equiv.) was azeotropically distilled
three times with toluene 13£50 ml) and dissolved in a
mixture of Et2O 15 ml) and per¯uorooctyle 15 ml). Triethyl-
amine 10.2ml, 1.16 mmol, 4.0 equiv.) was added to this
5.4.7. Trisꢀ2-ꢀ1H,1H,2H,2H-per¯uorodecyl)phenyl)phos-
phite ꢀA). The 2-11H,1H,2H,2H-per¯uorodecyl)phenol
15.55 mmol, 3.0 equiv.) was azeotropically distilled with

T. Mathivet et al. / Tetrahedron 58 ;2002) 3877±3888
3887
solution. Phosphorus trichloride 10.03 ml, 0.40 mmol,
1.3 equiv.) dissolved in 5 ml of Et2O was added dropwise
at 08C for 1 h under N2 to the stirred solution of 2,4-
bis11H,1H,2H,2H-per¯uorodecyl)phenol. Subsequently the
reaction mixture was stirred for 4 h at room temperature.
The amine salts formed were removed by ®ltration over
dried silica gel under N2 with further 40 ml of Et2O. The
solvent was removed in vacuo to afford the pure phosphite
1C). Yield: 0.801 g 193%) of a white solid mp: 548C NMR
31P{1H} 1CF2ClCCl2F, external lock on CDCl3) d 1ppm):
1129.87 1s); NMR 1H 1CF2ClCCl2F, external lock on
CDCl3) d 1ppm): 7.22 1d, 3H, Jˆ8.3 Hz, 3£6-ArH), 7.09
1d, 3H, Jˆ1.8 Hz, 3£3-ArH), 7.06 1dd, 3H, Jˆ8.3 and
1.8 Hz, 3£5-ArH), 2.87 1m, 12H, 6£±CH2±CH2±C8F17),
2.32 1m, 12H, 6£±CH2±CH2±C8F17); NMR 19F{1H}
1diethylether, external lock on CDCl3) d 1ppm): 281.06
then started 11500 rpm) and the autoclave was pressurized
with 40 atm of CO/H2 11/1) from a gas reservoir connected
to the reactor through a high pressure regulator valve allow-
ing to keep constant the pressure in the reactor throughout
the whole reaction. The reaction medium was sampled
during the reaction for GC analyses of the organic phase
after decantation. For kinetic measurements the time corre-
sponding to the addition of CO/H2 was considered as the
beginning of the reaction.
5.7. Recycling experiments
The ®rst batch was carried out as described above. After
10 min of reaction time, the autoclave was cooled rapidly
to room temperature and carefully depressurized. The reac-
tion solution was transferred to nitrogen ®lled Schlenk tube.
After 30 min, the ¯uorous and organic phases were sepa-
rated and a new carefully deoxygenated solution of ole®n
177.4 mmol) and undecane 17.74 mmol) was introduced in
the Schlenk tube. The resulting mixture was charged under
an atmosphere of N2 into the autoclave and used in another
hydroformylation run as described above.
3
1t, 18F, JFFˆ9.3 Hz, 6£±CF3), 2114.921m, 6F, 3 £
±CF2± in g of 4-C arom), 2115.15 1m, 6F, 3£±CF2± in g
of 2-C arom), 2122.22 1m, 36F, 18£±CF2±), 2123.04 1m,
6F, 3£±CF2±), 2123.22 1m, 6F, 3£±CF2±), 2123.91 1m,
12F, 6£±CF2±), 2126.40 1m, 6F, 3£±CF2±), 2126.64 1m,
6F, 3£±CF2±); NMR 13C{1H} 1CF2ClCCl2F, external lock
on CDCl3) d 1ppm): 149.35 1s, 1-C arom), 136.68 1s, 4-C
arom), 131.70 1br s, 2-C arom), 131.26 1s, 3-CH arom),
3
128.55 1s, 5-CH arom), 120.92 1d, JCPˆ12.5 Hz, 6-CH
Acknowledgements
2
arom), 33.71 1t, JCFˆ22.1 Hz, ±CH2±CH2±C8F17 in b of
4-C arom), 31.93 1t, 2JCFˆ22.1 Hz, ±CH2±CH2±C8F17 in b
of 2-C arom), 26.41 1br s, ±CH2±CH2±C8F17 in a of 4-C
arom), 22.32 1br s, ±CH2±CH2±C8F17 in a of 2-C arom),
105±120 1complex signals of CF2± and ±CF3); MS
1MALDI) m/z: 2986 1M1); IRFT 1KBr) n 1cm21): 1496
1m), 1457 1w), 1373 1w), 1333 1m), 1240 1vs), 1205 1vs),
1148 1vs), 1135 1s), 1115 1s), 1084 1m), 971 1w), 871 1w),
704 1w), 656 1w).
This research was supported by funds from the Centre
National de la Recherche Scienti®que 1CNRS) and Ato®na.
We would like also to thank Ato®na for kind gifts of
¯uorinated chemicals.
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