EP1150987A1

EP1150987A1 - Tris (1h,1h, 2h,2h-perfluoroalkyl) aryl]phosphites and catalytic uses thereof

Info

Publication number: EP1150987A1
Application number: EP00903765A
Authority: EP
Inventors: Jean-Luc Couturier; Thomas Mathivet; Eric Monflier; Yves Castanet; André Mortreux
Original assignee: Centre National de la Recherche Scientifique CNRS
Current assignee: Centre National de la Recherche Scientifique CNRS
Priority date: 1999-02-10
Filing date: 2000-02-09
Publication date: 2001-11-07
Also published as: FR2789391A1; FR2789391B1; WO2000047590A1; US6534684B1

Abstract

The invention concerns a method for preparing tris[(1H,1H, 2H,2H-perfluoroalkyl) aryl]phosphites. Said method consists in preparing a grignard reagent from an alkoxyhalogenobenzene, then in reacting it with a iodo-1H,1H,2H, 2H-perfluoroalkane; in transforming the alkoxy function of (1H,1H, 2H,2H-perfluoroalkyl) alkoxybenzene obtained into a hydroxy function, then in reacting (1H,1H, 2H,2H-perfluoroalkyl) hydroxybenzene with PCl3. The invention also concerns said fluorinated arylphosphites and their use as transition metal ligand for making catalysts to be used in two-phase catalysis with fluorinated phase.

Description

TRIS [(1H.1H, 2H.2H-PERFLUOROAL YL) ARYL] PHOSPHITES AND THEIR APPLICATIONS IN CATALYSIS

TECHNICAL AREA

The present invention relates to a process for the preparation of tris- [(1 H, 1 H, 2H, 2H-perfluoroalkyl) aryl] phosphites, hereinafter fluorinated arylphosphites.

The present invention also relates to said fluorinated arylphosphites and their applications in particular in biphasic catalysis with a fluorinated phase.

PRIOR ART

This biphasic catalysis with a fluorinated phase has been described by Istvan T. Horwath et al. in US patent 5,463,082.

The general concept of this catalysis is based on the use of an immiscible fluorinated phase with an organic phase when cold and generally miscible when hot.

The fluorinated phase is a solvent rich in C-F bonds (fluorocarbons, hydrofluorocarbons).

When cold, the system consists of two phases: - a fluorinated phase which is a solvent rich in C-F bonds and which contains a catalyst made soluble in said fluorinated solvent via fluorinated chains,

- an organic hydrocarbon phase, immiscible with the fluorinated phase, which contains the reagents. The catalysis reaction is carried out hot in a generally homogeneous phase, that is to say that above a certain temperature, a single phase is generally obtained in which the catalysis takes place. When the reaction is complete, the catalyst is easily recovered by cooling the reaction medium to a temperature below the miscibility temperature of the two phases.

Thus, in order to make the catalyst preferentially soluble in the fluorinated phase, it has been recommended to functionalize it with one or more perfluoroal yl groups. The perfluoroalkyl groups of fluorinated phosphites used as coordination ligands have electron-withdrawing properties which can influence the coordination characteristics of the phosphorus atom and thus adversely modify the catalytic activity of the catalysts produced from such fluorinated ligands.

To reduce these undesirable effects of perfluoroalkyl chains on the phosphorus atom, it has been proposed to introduce non-fluorinated groups designated "spacers" between the phosphorus atom and said perfluoroalkyl chain. As examples of such spacers, mention may be made of polymethylene radicals (CH2) _n with n ranging from 1 to 3 and the phenylene radical -CeH -.

By way of illustration of fluorinated phosphites containing such spacers, mention will be made of the tris (1 H, 1 H, 2H, 2H-perfluoroalkyl) phosphite mentioned by I. T. Horwath et al. in US patent 5,463,082; the tris (4-tridecafluorohexylphenyl) phosphite mentioned by E.G. Hope et al. in J. Chem. Soc. Perkin Trans. 1. 1997, pages 3609-3612, the tris (perfluoroalkylphenyl) phosphites mentioned by T. Mathivet et al. in Tetrahedron Letters 39, 1998, pages 9411-9414.

In general, these fluorinated phosphites are obtained with low yields, by processes involving expensive reagents and with long reaction times (several days) in particular, for arylphosphites with perfluoroalkyl chains.

Thus, for example, EG Hope et al. (J. Chem. Soc. Perkin Trans. 1, 1997, pages 3.609-3.612) obtain the tris (4-tridecafluorohexylphenyl) phosphite by synthesizing in a first step 4-tridecafluorophenol by reaction of C ₆ F ₁₃ 1 in solution in l hexafluorobenzene on paraiodophenol in the presence of copper in DMSO at 80 ° C, under nitrogen for 6 days. In a second step, 4-tridecafluorophenol, obtained with a yield of 63%, is introduced slowly with triethylamine into a solution of PCI ₃ in Et 0. The tris (4-tridecafluorohexylphenyl) phosphite is obtained with a yield of 55, 7%, or an overall yield of 35%.

Mathivet et al. (Tetrahedron Letters, 39, 1998, pages 9411-9414) also use to obtain (perfluoroalkyl) phenols the reaction of a perfluoroalkyl iodide on bromo- or iodophenol but they operate in the DMSO. They obtain the (perfluoroalkyl) phenols with yields ranging from 23% for 2-methyl-4-perfluorooctylphenol to 70% for 4-perfluorooctylphenol.

The application of the reaction between an iodo- or bromophenol and an iodoperfluoroalkyl in the presence of copper (so-called Ullmann reaction) does not allow the introduction of 1 H, 1 H, 2H, 2H-2H-perfluoroalkyl groups on the nucleus phenolic.

Japanese patent application JP 7-179384 describes the production of 4- (1 H, 1 H, 2H, 2H-perfluoroalkyl) phenol by carrying out the following reactions: - reaction of an alcohol CF ₃ (CF2) pCH ₂ CH2θH with triflic acid to lead to an ester of formula: CF3 (CF ₂ ) pCH ₂ CH2θSθ2CF3 (with p = 1 to 15),

- then reaction of said ester with a Grignard reagent obtained from magnesium and a p-alkoxyhalogenobenzene to yield 4- (1 H, 1 H, 2H, 2H-perfluoroalkyl) alkoxybenzene and after cleavage of the alkoxy function to obtain 4- (1H, 1H, 2H, 2H-perfluoroalkyl) phenol with yields close to 50%.

However, this operating method has the drawback of using expensive reagents: CF ₃ (CF ₂ ) pCH ₂ CH ₂ OH alcohols and triflic acid, the latter being moreover difficult to handle. STATEMENT OF THE INVENTION

We have now found a process for the preparation of tris- [(1 H, 1 H, 2H, 2H-perfluoroalkyl) phenyl] phosphites of formula (I):

in which the (5-x) R, identical or different, represent a hydrogen atom, an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 10; a halogen atom such as bromine or chlorine; Rf represents a radical 1H, 1H, 2H, 2H-perfluoroalkyl C _n F _{2n +} ι C ₂ H ₄ - with n ranging from 4 to 20, and preferably ranging from 8 to 20, x is a number integer ranging from 1 to 5, and preferably ranging from 1 to 3; characterized in that it comprises the stages consisting in: a) preparing a Grignard reagent of formula (II)

from an alkoxyhalobenzene of formula (III):

in the formulas of which, R ¹ represents a radical, alkyl, linear or branched, having a number of carbon atoms ranging from 1 to 6 and preferably ranging from 1 to 3, X represents a bromine, chlorine atom or iodine, R and x having the same meanings as in formula (I), then reacting said compound (II) with a 1-iodo-1 H, 1 H, 2H, 2H-perfluoroalkane C _n F _{2n +} ι C ₂ H ₄ I (IV), below represents by Rfl, to obtain a (1 H, 1 H, 2H, 2H- perfluoroalkyl) alkoxybenzene (V):

c) transforming the alkoxy function R ¹ 0- of (V) obtained in step a) into a hydroxyl function HO ^" to obtain a (1 H, 1 H, 2H, 2H ^" perfluoroalkyl) hydroxybenzene of formula (VI):

d) reacting the compound (VI) obtained in step b) with PCI ₃ to obtain the tris [(1 H, 1 H, 2H, 2H-perfluoroalkyl) phenyl] phosphite (I).

The Grignard reagent (II) is obtained according to methods known to a person skilled in the art which consist in reacting an alkoxyhalobenzene of formula (III) with magnesium in an ethereal solvent such as diethyl ether or THF at room temperature.

Preferably X represents a bromine atom. By way of illustration of bromoalkoxybenzenes which can be used according to the present invention, mention will be made of 4-bromoanisole, 3-bromoanisole, 2,4-dibromoanisole, 2,4,6-tribromoanisole, 4-bromo-2,6- dimethylanisole, 4-bromophenetole.

The reaction between the Grignard reagent (II) and the iodofluorinated compound Rfl is carried out in the presence of copper iodide Cul used in weight amounts ranging from 0.1% to 10% relative to the compound Rfl.

In a preferred manner, the ethereal solution of the Grignard reagent is slowly introduced into an ethereal suspension of Rfl plus Cul at a temperature in the region of 0 ° C., then, when the addition is complete, the reaction medium is kept brought to 20-30 ° C with stirring for a period at most equal to 6 hours and, preferably between 1 and 3 hours.

Then the medium is hydrolyzed and the compound (V) is isolated according to methods known to those skilled in the art (extraction, washing, drying, removal of the solvent under reduced pressure).

By way of illustration of Rfl that can be used according to the present invention, mention will be made of 1-iodo-1 H, 1 H, 2H, 2H-perfluorodecane CF ₃ (CF ₂ ) 7CH ₂ CH ₂ I, 1-iodo 1 H, 1 H, 2H, 2H-perfluorooctane CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ I.

The cleavage of the alkoxy function R ¹ 0 of the compound (V), step b), is carried out by methods known to those skilled in the art, in particular by means of boron tribromide BBr ₃ in an organic solvent such as benzene or toluene at a temperature between 60 ° C and 100 ° C and preferably between 70 ° C and 90 ° C.

The reaction medium obtained is then cooled and then introduced into water. The hydroxylated compound (VI) is isolated in a known manner.

According to the process of the present invention BBr ₃ is used according to a compound (V) / BBr ₃ molar ratio of between 1 and 1.5, and preferably between 1, 2 and 1, 4. The reaction between compound (VI) and PCI ₃ , step c), is carried out in an organic solvent such as THF or diethyl ether Et 0, in the presence of a tertiary base such as pyridine or triethylamine.

The operation is carried out at low temperature, -10 ° C. to 0 ° C., by introducing PCI ₃ into a medium containing an organic solvent, the tertiary base and the fluorinated phenolic compound (VI).

When the addition is complete, the temperature of the reaction medium is allowed to rise to + 20 ° C, + 30 ° C and then the medium is kept at this temperature with vigorous stirring for a few hours. Then the fluorinated arylphosphite (1) is filtered and isolated from the filtrate by removing the organic solvent under reduced pressure.

The compounds obtained during steps a), b) and c) can be identified by elementary analysis, by proton NMR, ¹⁹ F, ³ C and ³¹ P and by mass spectrometry (MS). The process according to the present invention has the advantage of obtaining fluorinated arylphosphites (I) with good yields from commercially available reagents.

Another subject of the invention relates to tris [(1H, 1H, 2H, 2H- perfluoroalkyl) phenyl] phosphites of formula (I) described above. Among the compounds of formula (I), those in which x = are preferred

1, 2 or 3, R = H or CH ₃ -, Rf = CF ₃ (CF ₂ ) ₇ C ₂ H ₄ -.

By way of illustration of such compounds, particular mention will be made

• the tris [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite, ^» the tris [2- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite, • the tris [ 2,4-bis (1H, 1H, 2H, 2H-perfluorodecyl) phenyl] phosphite,

• or the tris [3- (1 H, 1 H, 2H, 2H-perfluoroalkyl) -5-chlorophenyl] phosphite, particularly preferred and the manufacturing process and spectroscopic characteristics of which are detailed in Examples 1 to 4 below . The fluorinated arylphosphites (I) are resistant to hydrolysis and very soluble in perfluoric solvents which makes it possible to use them advantageously as ligands for transition metals to produce catalysts which can be used in particular in biphasic catalysis with a phase fluorinated to perform chemical reactions of hydroformylation, hydrogenation of unsaturated compounds, carbonylation, telomerization and cyclodimerization of dienes, hydrocyanation of olefins or conjugated dienes. Another object of the invention is therefore the use of tris [(1 H, 1 H, 2H, 2H- perfluoroalkyl) phenyl] phosphites of formula (I) as ligands of transition metals for the production of catalysts for the reactions previously mentioned chemicals.

Examples of transition metals which can be used according to the present invention include rhodium, palladium, ruthenium, nickel, iridium, chromium, cobalt, iron.

The catalysts obtained with fluorinated phosphites (I) of the present invention used as ligands have the advantage of being easily separated and recycled when they are used in fluorinated biphasic catalysis. In addition, the Applicant has found that during the hydroformylation reaction of olefins, and in particular, during the hydroformylation of dec-1-ene with a catalyst of the rhodium type complexed with tris [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite, said catalyst could be recycled without loss of catalytic activity. The catalyst according to the present invention can be prepared in situ, that is to say in the reactor where the chemical reaction takes place by mixing the transition metal generally in the form of a metal complex or a metal salt with the compounds. of formula (I) obtained according to the process of the present invention, or it can be prepared, and isolated separately. The following examples illustrate the invention.

EXAMPLES The following reagents are used:

- Magnesium powder (sold by the company ALDRICH)

- anhydrous THF distilled over sodium / benzophenone under an inert gas atmosphere (nitrogen)

- bromoanisole (ALDRICH) for the synthesis of Example 1

- 2-bromoanisole (ALDRICH) for the synthesis of Example 2

- 3,5-dichloroanisole (ALDRICH) for the synthesis of Example 3 - 2.4 dibromoanisole (ALDRICH) for the synthesis of Example 4 -1-iodo-1 H, 1 H, 2H, 2H-perfluorodecane, sold by the company ELF

ATOCHEM S.A. under the designation FORALKYL EI-8 (examples 1 to 4)

- Ass (ALDRICH) - Silica gel, 70-230 mesh, 60 Â (ALDRICH)

- BBr ₃ (ALDRICH)

- PCI ₃ (ALDRICH)

- Triethylamine (sold by the company ACROS) distilled on CaH under nitrogen - Rh (acac) (CO) ₂ for Rh (acetylacetonate) (CO) ₂ (ALDRICH)

- dec-1-ene (ACROS)

- n-undecane (ACROS)

The compounds obtained were characterized by elementary analysis and by ¹ H, ¹³ C, ³¹ P and ¹⁹ F NMR. The NMR spectra were carried out on a BRUKER AC device.

100 ( ¹ H, 100 MHz; ³¹ P, 40.53 MHz; ¹⁹ F, 94.22 MHz; ¹³ C, 25.18 MHz). The ¹³ C and ³¹ P NMRs are carried out with ¹ H decoupling.

The chemical shifts δ are given in ppm, relative to tetramethylsilane (internal reference) for the proton and carbon, compared to H ₃ P0 ₄ at 85% (external reference) for phosphorus and relative to trifluoroacetic acid for fluorine.

In Tables 1 and following:

- S ald denotes the selectivity in aldehydes

- Isom denotes the selectivity in isomers of dec-1-ene - n means number of moles of linear aldehyde

- i means number of moles of aldehyde connected Example 1

Preparation of the tris [4- (1H, 1H, 2H.2H-perfluorodecyl) phenyllphosphite

a) Preparation of 4- (1H, 1H, 2H, 2H-perfluorodecyl) anisole.

In a 250 ml flask fitted with a reflux condenser and a side tube, 439 mg (18.06 mmol) of magnesium powder are dried under vacuum for 1 hour. We put the assembly under nitrogen. 25 ml of anhydrous THF are added. About half of the 3.375 g (18.06 mmol) of 4-bromoanisole is added under nitrogen to the suspension of Mg in THF, the remainder of 4-bromoanisole is diluted with 5 ml of THF. 2 or 3 drops of bromoethane are added to the flask containing the magnesium, the reaction starts instantly. The remainder of the 4-bromoanisole solution is poured dropwise over 15 minutes onto the Mg suspension. It is left to react for approximately 1 hour.

Then 10.356 g (18.06 mmol) of iodo-1 H, 1 H, 2H, 2H-2H-perfluorodecane and 340 mg (1.8 mmol) of copper iodide Cul are dissolved in 20 ml of anhydrous THF. The magnesian solution is poured dropwise at 0 ° C in 1 hour over the suspension of C8Fι ₇ C ₂ H l and Cul. The mixture is left to return to ambient temperature and is stirred for 3 hours.

Hydrolysis is carried out with a solution of 10 ml of 37% hydrochloric acid in 50 ml of water. The mixture is left stirring for 15 minutes. 50 ml of ether are added and the organic phase is recovered. The aqueous phase is extracted with 3 x 30 ml of ether. The organic phases are combined and washed with an aqueous solution of sodium thiosulfate (10 g of Na ₂ S ₂ 0 ₃ in 100 ml of water). The organic phase is then dried over sodium sulfate for 30 minutes, filtered and evaporated under reduced pressure.

The product is purified by column chromatography (h = 55 cm; 0 = 5 cm) of silica gel, (70-230 mesh, 60 Å) with a petroleum ether / dichloromethane (80/20) mixture as eluent (Rp = 0.67).

After evaporation of the identical fractions in TLC, 6.256 g of a white solid is obtained which has a melting point equal to 35 ° C. The yield in 4- (1 H, 1 H, 2H, 2H-perfluorodecyl) anisole is 65% relative to the 4-bromoanisole used.

¹ H NMR (CDCI ₃ ) δ (ppm): 7.13 (2H, m, J = 8.6 Hz, J '= 2.5 Hz, 3.5- ArH), 6.86 (2H, m, J = 8.6 Hz, J '= 2.5 Hz, 2.6-ArH), 3.79 (3H, s, -OCH ₃ ), 2.86 (2H, m, ³ J _HH = 8.4 Hz, -CH ₂ -CH ₂ -C ₈ F ₁₇ ), 2.33 (2H, tt, ³ J _HF = 18.3 Hz, ³ J _HH = 8.4 Hz, -CH ₂ -CH ₂ -C ₈ F ₁₇ ).

¹⁹ F NMR (CDCI3) δ (ppm): -81, 13 (3F, t, J = 9.5 Hz, -CF ₃ ), -114.99 (2F, t, J = 12.9 Hz, -CF ₂ -), -122.02 (2F, m, -CF ₂ -), -122.24 (4F, m, 2 x -CF ₂ -), - 123.04 (2F, m, -CF ₂ -) , -123.82 (2F, m, -CF ₂ -), -126.45 (2F, m, -CF ₂ -). ¹³ C NMR (CDCI ₃ ) δ (ppm): 154.32 (s, 1-C arom), 131, 51 (s, 4-C arom),

129.57 (s, 3.5-CH arom), 114.30 (s, 2.6-CH arom), 55.21 (s, -OCH ₃ ), 33.41 (t, ² J _C F = 22.0 Hz, -CH ₂ -ÇH ₂ -C ₈ F ₁₇ ), 25.69 (s, -ÇH ₂ -CH ₂ -C ₈ Fι ₇ ) + complex signals -CF - and -CF ₃ .

SM m / e: 554: M + (17.3%), 535: M + -F (6.3%), 134: M + -HC ₈ F ₁₇ (3.7%), 121: M + -CH ₂ C ₈ F ₁₇ (100%), 69: CF ₃ + (2.0%).

Elementary analysis calculated for C ₁ HιιF- | ₇ 0: C: 36.85%; H: 1.98%, found: C: 38.11%; H: 2.14%. b) Preparation of 4- (1H, 1H, 2H, 2H-perfluorodecyl) phenol.

Under nitrogen, 5.00 g (9.02 mmol) of 4- (1 H, 1H, 2H, 2H-perfluorodecyl) anisole are dissolved in 40 ml of anhydrous toluene. 1.1 ml (11.73 mmol) of boron tribromide are withdrawn from the syringe and diluted in 10 ml of anhydrous toluene. The BBr ₃ solution is poured in dropwise at room temperature in 15 minutes over the fluorinated anisole solution. The mixture is left under vigorous stirring for 2 hours at room temperature and then 2 hours at 80 ° C.

The mixture is allowed to return to ambient temperature and the reaction mixture is poured into 50 ml of water. 50 ml of ether are added, the phase is recovered organic. The aqueous phase is extracted with 3 times 30 ml of ether. The organic phase is then dried over sodium sulfate for 30 minutes, filtered and evaporated in vacuo.

Purification is carried out by column chromatography (h = 55 cm; 0 = 5 cm) of silica gel (70-230 mesh, 60 Å) with pure dichloromethane as eluent (R _F = 0.48).

After evaporation of the identical fractions in TLC, 3.799 g of a white solid is obtained which has a melting point of 88 ° C. The yield of 4- (1 H, 1 H, 2H, 2H-perfluorodecyl) anisole relative to the methoxy compound used is 78%.

¹ H NMR (CDCI ₃ ) δ (ppm): 7.08 (2H, m, J = 8.5 Hz, J '= 2.5 Hz, 3.5- ArH), 6.78 (2H, m, J = 8.5 Hz, J '= 2.5 Hz, 2.6-ArH), 4.75 (1 H, s, -OH), 2.84 (2H, m, ³ J _HH = 8.4 Hz, -CH ₂ -CH ₂ -C ₈ F ₁₇ ), 2.32 (2H, tt, ³ J _HH = 18.3 Hz, ³ J _HH = 8.4 Hz, -CH ₂ -CH ₂ -C ₈ F ₁₇ ). ¹⁹ F NMR (CDCI3) δ (ppm): -81.08 (3F, t, J = 9.7 Hz, -CF ₃ ), -114.93 (2F, t,

J = 12.5 Hz, -CF ₂ -), -121, 99 (2F, m, -CF ₂ -), -122.21 (4F, m, 2 x -CF ₂ -), -123.00 ( 2F, m, -CF ₂ -), -123.78 (2F, m, -CF ₂ -), -126.41 (2F, m, -CF ₂ -).

¹³ C NMR (CDCI3) δ (ppm): 154.32 (s, 1-C arom), 131, 51 (s, 4-C arom), 129.57 (s, 3.5-CH arom), 115 , 69 (s, 2,6-CH arom), 33.31 (t, ² J _CF = 21.8 Hz, - CH ₂ -ÇH ₂ -C ₈ F ₁₇ ), 25.67 (s, -ÇH ₂ -CH ₂ -C ₈ F ₁₇ ) + complex signals -CF ₂ - and - CF ₃ .

SM m / e: 540: M + (4.7%), 521: M ⁺ -F (2.5%), 120: M ⁺ -H -C ₈ F ₁₇ (3.1%), 107: M + - CH ₂ C ₈ F ₁₇ (100%), 69: CF ₃ ⁺ (0.5%).

Elementary analysis calculated for Cι ₆ H ₉ F- | ₇ 0: C: 35.58%; H: 1.66%, found C: 36.63%; H: 1.80%. c) Obtaining the tris [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite

3 g of 4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenol are dried by azeotropic distillation with 50 ml of toluene (distilled on sodium / benzophenone under nitrogen) at atmospheric pressure and under nitrogen. We put the solid under vacuum

(about 4 hours) while heating with a hairdryer from time to time to remove traces of residual toluene, until constant mass.

0.2 ml of PCI ₃ phosphorus trichloride (332.6 mg; 2.42 mmol) is weighed under nitrogen and diluted with 15 ml of THF.

It is cooled to 0 ° C. using an ice bath and the PCI ₃ solution is poured in 1 hour and 30 minutes dropwise under nitrogen onto the phenolic solution. The mixture is left under vigorous stirring at room temperature for 4 hours.

A ligand filtration assembly is prepared on silica. The silica stored in an oven is drawn off under vacuum at 100 ° C., while heating the assembly with a hair dryer. The assembly is placed under nitrogen, the crude reaction is transferred to the silica and eluted with 40 ml of THF. The filtrate obtained is evaporated under vacuum, to constant mass.

2.969 g of tris [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] - phosphite are obtained, which is in the form of a white solid, melting at 83 ° C. The yield is 97%. ³¹ P NMR (CDCI ₃ ) δ (ppm): +127.95.

¹ H NMR (CDCI3) δ (ppm): 7.16 (2H, m, J = 8.7 Hz, J '= 2.5 Hz, 3.5 ArH), 7.10 (2H, m, J = 8.7 Hz, J '= 2.5 Hz, 2.6 ArH), 2.89 (2H, m, ³ J _H H = 8.4 Hz, -CH ₂ -CH ₂ -C ₈ F ₁₇ ), 2.34 (2H, tt, 3ϋ _HF = 18.1 Hz, ³ J _HH = 8.4 Hz, -CH ₂ -CH ₂ -

^C 8 ^F 17) - ¹⁹ F NMR (CDCI3) δ (ppm): -81, 61 (9F, t, J = 9.7 Hz, 3 x -CF ₃ ),

1 15.19 (6F, t, J = 12.8 Hz, 3 x -CF ₂ -), -122.24 (6F, m, 3 x -CF ₂ -), -122.49 (12F, m, 6 x -CF ₂ -), -123.32 (6F, m, 3 x -CF ₂ -), -124.02 (6F, m, 3 x -CF ₂ -), -126.82

(6F, m, 3 x -CF ₂ -).

¹³ C NMR (CDCI3) δ (ppm): 150.46 (d, ² J _CP = 2.9 Hz, 1 -C arom), 133.35 (s, 4-C arom), 129.69 (s, 3,5-CH arom), 121, 16 (d, ³ J _CP = 6.7 Hz, 2.6-

CH arom), 33.16 (t, ² J _CF = 22.0 Hz, -CH ₂ -ÇH ₂ -C ₈ F ₁₇ ), 25.92 (s, -ÇH ₂ -CH ₂ -

C ₈ F ₁₇ ) + complex signals -CF ₂ - and -CF ₃ . Elemental analysis% calculated for C ₄₈ H ₂₄ F ₅₁ 0 ₃ P: C: 34.98%; H: 1.45%, found: C: 35.67%; H: 1.60%.

Examples 2 to 4

Preparation of the trisfë-d H. 1 H. 2H. 2H-perfluorodecvhphenyllphosphite. trisr3-chloro-5- (1 H, 1 H, 2H. 2H-perfluorodecyl) phenylphosphite and trisr2,4-bis (1 H, 1 H 2H. 2H-perfluorodecyl) phenyllphosphite

The three phosphites mentioned above were synthesized according to a procedure similar to that described in Example 1.

Characteristics of phosphites: tris [2- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite (Example 2)

White solid melting at 68 ° C

³ P { ¹ H} NMR (CDCI ₃ ) δ (ppm): + 132.71 (s).

¹ H NMR (CDCI ₃ ) δ (ppm): 7.22 (3H, br d, J = 8.0 Hz, 3 x 3-ArH), 7.18 (6H, um, 3 x 4 and 5-ArH ), 7.09 (3H, m, J = 8.0 Hz, 3 x 6-ArH), 2.85 (6H, m, ³ J _HH = 8.2 Hz, 3 x -CH ₂ -CH ₂ - C ₈ F ₁₇ ), 2.26 (6H, tt, ³ J _H F = 18.4 Hz, ³ J _H = 8.2 Hz, 3 x - CH ₂ -CH ₂ -C ₈ Fι).

¹⁹ F NMR { ¹ H} (CDCI3) δ (ppm): -81, 39 (9F, t, ³ J _FF = 9.8 Hz, 3 x -CF ₃ ), - 115.49 (6F, um, 3 x -CF ₂ - in α of -CH ₂ -), -122.28 (6F, um, 3 x -CF ₂ -), -122.49 (12F, um, 6 x -CF ₂ -), -123 , 29 (6F, um, 3 x -CF ₂ -), -123.97 (6F, um, 3 x -CF ₂ -), - 126.71 (6F, um, 3 x -CF ₂ -).

NMR ¹³ C { ¹ H} (CDCI ₃ ) δ (ppm): 149.93 (d, ² J _C p = 3.0 Hz, 1-C arom),

130.79 (s, 3-CH arom), 130.60 (d, ³ J _C p = ^1.9 Hz, 2-C arom), 128.27 (s, 5-CH arom), 124.79 ( s, 4-CH arom), 119.86 (d, ³ J _CP = 13.3 Hz, 6-CH arom), 31, 15 (t, ² J _CF = 22.0 Hz, -CH ₂ -ÇH ₂ -C ₈ F ₁₇ ), 21, 57 (t, ³ J _CF = 3.8 Hz, -ÇH ₂ -CH ₂ -C ₈ F ₁₇ ) + complex signals -CF ₂ - and -CF ₃ (105 - 120) . - tris [3- (1 H.1 H, 2H.2H-perfluorodecyl) -5-chlorophénvnphosphite (example 3) White solid melting at 58 ° C

³¹ P NMR { ¹ H} (CDCI ₃ ) δ (ppm): + 126.53 (s).

¹ H NMR (CDCI ₃ ) δ (ppm): 7.02 (6H, um, 3 x 2 and 4-ArH), 6.82 (3H, um, 3 x 6-ArH), 2.86 (6H, m, ³ J _H = 8.3 Hz, 3 x -CH2-CH ₂ -C ₈ F ₁₇ ), 2.32 (6H, m, ³ J _H = 18.1 Hz, ³ J _HH = 8.3 Hz , 3 x -CH ₂ -CJH2-C ₈ F ₁₇ ).

¹⁹ F NMR { ¹ H} (CDCI ₃ ) δ (ppm): -81, 10 (9F, t, ³ J _FF = 9.8 Hz, 3 x -CF ₃ ), - 114.91 (6F, um, 3 x -CF ₂ - in α of -CH ₂ -), -122.04 (6F, um, 3 x -CF ₂ -), -122.26 (12F, um, 6 x -CF ₂ -), - 123.07 (6F, um, 3 x -CF ₂ -), -123.74 (6F, um, 3 x -CF ₂ -), - 126.48 (6F, um, 3 x -CF ₂ -).

NMR ¹³ C {H} (CDCI ₃ ) δ (ppm): 152.00 (d, ² J _CP = 2.4 Hz, 1-C arom), 142.63 (s, 5-C arom), 135, 51 (s, 3-C arom), 124.97 (s, 4-CH arom), 119.55 (d, ³ J _C p = 7.3 Hz, 2-CH arom), 119.03 (d, ³ J _CP = 6.4 Hz, 6-CH arom), 32.49 (t, ² J _CF = 22.1 Hz, -CH ₂ -ÇH ₂ -C ₈ F ₁₇ ), 26.27 (t, ³ J _C F = 3.3 Hz, -ÇH ₂ -CH ₂ -C ₈ F ₁₇ ) + complex signals -CF ₂ - and -CF ₃ (105 - 120).

- tris [2,4-bis (1 H. 1 H. 2H, 2H-perfluorodecyl) phenylphosphite (example 4)

White solid melting at 54 ° C.

RMN 3 ^J 1 ¹ rP -) {f1Ηι} (CF ₂ CICCI ₂ F, external lock on CDCI3) δ (ppm): + 129.87 (s). ¹ H NMR (CF ₂ CICCI ₂ F, external lock on CDCI3) δ (ppm): 7.22 (3H, d, J = 8.3 Hz, 3 x 6-ArH), 7.09 (3H, d, J '= 1.8 Hz, 3 x 3-ArH), 7.06 (3H, dd, J = 8.3 Hz, J '= 1.8 Hz, 3 x 5-ArH), 2.87 (12H, um, 6 x -CH ₂ -CH ₂ -C ₈ Fι ₇ ), 2.32 (12H, um, 6 x -CH ₂ -CH ₂ -C ₈ F ₁₇ ).

RMN ¹⁹ F { ¹ H} (diethyl ether, external lock on CDCI ₃ ) δ (ppm): -81, 06 (18F, t, ³ J _FF = 9.3 Hz, 6 x -CF ₃ ), -114.92 (6F, um, 3 x -CF - in γ of 4-C arom), - 115.15 (6F, um, 3 x -CF ₂ - in γ of 2-C arom), -122.22 (36F, um , 18 x -CF ₂ -), - 123.04 (6F, um, 3 x -CF ₂ -), -123.22 (6F, um, 3 x -CF ₂ -), -123.91 (12F, um, 6 x - CF ₂ -), -126.40 (6F, um, 3 x -CF ₂ -), -126.64 (6F, um, 3 x -CF ₂ -).

RMN ¹³ C { ¹ H} (CF ₂ CICCI ₂ F, external lock on CDCI ₃ ) δ (ppm): 149.35 (s, 1-C arom), 136.68 (s, 4-C arom), 131 , 70 (br s, 2-C arom), 131, 26 (s, 3-CH arom), 128.55 (s, 5-CH arom), 120.92 (d, ³ J _CP = 12.5 Hz , 6-CH arom), 33.71 (t, ² J _CF = 22.1 Hz, -CH ₂ -ÇH ₂ -C ₈ F ₁₇ in β of 4-C arom), 31, 93 (t, ² J _CF = 22.1 Hz, - CH ₂ - H ₂ -C ₈ Fi7 in β of 2-C arom), 26.41 (br s, -ÇH ₂ -CH ₂ -C ₈ F ₁₇ in α of 4-C arom), 22.32 (br s, -ÇH ₂ -CH ₂ -C ₈ Fι ₇ in α of 2-C arom) + complex signals - CF ₂ - and -CF ₃ (105 - 120).

Example 5

Hydroformylation of dec-1-ene in a fluorinated biphasic medium.

Reaction

CHO

CgH-jyCH = CH ₂ CO / Hp ^C 8 ^H 17. ^{+ C} 8 ^H 17-

-CHO linear aldehyde connected aldehyde

- isomers: dec-2-ene / dec-3-ene / dec-4-ene / dec-5-ene solvent: C ₈ F ₁₇ H

10.0 mg (38.7 μmol) of Rh (acac) (CO) and 319.0 mg (0.193 mmol) of tris are dissolved under nitrogen [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl ] phosphite in 15 ml of C ₈ F- | ₇ H (degassed 3 times in a row by freezing). The mixture is left under vigorous stirring for approximately 2 hours (until the rhodium is completely dissolved).

Weigh 10.856 g (77.4 mmol) of dec-1-ene and 1.2671 g (8.1 mmol) of n-undecane (internal standard for analyzes by gas chromatography). It is degassed 3 times in succession by freezing. This solution and the catalytic solution are combined.

This mixture is introduced under nitrogen into a 50 ml autoclave previously placed under nitrogen. The heating is adjusted to 80 ° C., the stirring at 1500 rpm and the pressure at 40 bars of CO / H ₂ (1: 1). The pressure is kept constant throughout the reaction by means of a ballast.

Samples are taken regularly to monitor the progress of the reaction, the results are collated in Table 1 below. The initial activity of the system is 2100 h ^"1 .

Examples 6 to 8

Hydroformylation of dec-1-ene in a fluorinated biphasic medium in the presence of tris [2- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenvnphosphite (Example 6), of trisf3-chloro-5- (1 H 1 H 2H, 2H-perfluorodécvQ phenyllphosphite (example 7) and trisl2.4-bis (1 H 1 H, 2H, 2H-perfluorodécyl) phenvnphosphite (example 8)

The hydroformylation of dec-1-ene was carried out using the three phosphites mentioned above using the same procedure as in Example 5; the results are collated in table 2.

TABLE 2 Example 9

Recycling of fluorinated catalytic phases in the presence of tris | 4- (1 H, 1 H. 2H. 2H-perfluorodecyl) phenyrjphosphite:

At the end of the catalytic test of Example 5, the autoclave is cooled in a cold water bath, depressurized, then returned to nitrogen. The catalytic solution is transferred under nitrogen into a Schlenk tube, the organic phase is separated by decantation 30 minutes later. Similar amounts of decene and undecane are again weighed and then added to the recycled fluorinated phase. The recycling test is then carried out in the same manner as above. The recycling results are collated in Table 3 below. The initial activity of the system is maintained at 2100 h ^"1 .

TABLE 3 Two additional recycling operations were carried out under the conditions defined above, the results are collated in Tables 4 and 5 below.

TABLE 5

Examples 10-11

Recycling in the presence of tris [2- (1 H, 1 H, 2H, 2H- perfluorodécvDphénvπ phosphite and trisr2.4-bis (1H. 1 H, 2H. 2H- perfluorodécvQphénvπphosphite

At the end of the catalytic tests of Examples 6 and 8, three recycling tests were carried out under the same conditions as in Example 9. The results obtained during the third recycling are shown in Table 6 below

TABLE 6 Examples 12 to 14

Hydroformylation of internal fatty olefins in a fluorinated biphasic medium in the presence of tris | 4- (1 H, 1 H, 2H, 2H-perfluorodécvDényllphosphite.

The hydroformylation of olefins with an internal double bond was carried out under the same conditions as in Examples 6-8 in the presence of tris [4- (1H, 1H, 2H, 2H-perfluorodecyl) phenyl] phosphite, the results are gathered in table 7.

TABLE 7

Claims

CLAIMS 1. Process for the preparation of of formula:

in which the (5-x) R, identical or different, represent a hydrogen atom, an alkyl radical, linear or branched having a number of carbon atoms ranging from 1 to 10, a bromine atom, an atom of chlorine, Rf represents a radical 1 H, 1 H, 2H, 2H-perfluoroalkyl C _n F _{2n + 1} C ₂ H ₄ - with n ranging from 4 to 20, x is an integer ranging from 1 to 5; characterized in that it comprises steps consisting in: a) preparing a Grignard reagent of formula (II)

from an alkoxyhalobenzene of formula (III):

in the formulas of which, R ¹ represents an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 6, X represents a bromine, chlorine or iodine atom, R and x having the same meanings that in formula (I), then reacting said compound (II) with a 1-iodo- 1 H, 1 H, 2H, 2H-perfluoroalkane C _n F _{2n + 1} C ₂ H ₄ l (IV) ( Rfl) to obtain a (1H, 1H, 2H, 2H-perfluoroalkyl) alkoxybenzene of formula (V):

b) transforming the alkoxy function R ¹ 0- of (V) obtained in step a) into a hydroxyl function HO ^" to obtain a (1H, 1H, 2H, 2H- perfluoroalkyl) hydroxybenzene of formula (VI):

c) reacting the compound (VI) obtained in step b) with PCI ₃ to obtain the tris [(1H, 1H, 2H, 2H-perfluoroalkyl) phenyl] phosphite (I).

2. Method according to claim 1 characterized in that in the formula (I) x ranges from 1 to 3, that n in the radical Rf ranges from 8 to 20 and that in the formulas (III) and (II), X represents a bromine atom and R ¹ is an alkyl radical having a number of carbon atoms ranging from 1 to 3.

3. Method according to one of claims 1 or 2, characterized in that the reaction between the Grignard reagent (II) and the iodofluorinated compound Rfl (IV), step a), is carried out in a solvent medium in the presence of Cul .

4. Method according to one of claims 1 to 3, characterized in that the iodofluorinated compound Rfl (IV) is 1-iodo-1H, 1H, 2H, 2H-perfluorodecane or 1-iodo-i, 1 H, 2H, 2H-perfluorooctane.

5. Method according to any one of claims 1 to 4, characterized in that the cleavage of the alkoxy function R ¹ 0-, step b), is carried out by means of boron tribromide in an organic solvent at a temperature included between 60 ° C and 100 ° C.

6. Method according to any one of claims 1 to 5, characterized in that the reaction between PCI ₃ and the compound (VI), step c), is carried out in an organic solvent in the presence of a tertiary base.

7. Tris [(1H, 1H, 2H, 2H-perfluoroalkyl) phenyl] phosphites of formula (I).

8. Compounds according to claim 7, characterized in that in the formula (I) x ranges from 1 to 3, R represents a hydrogen atom or CH ₃ -, Rf = CF3 (CF) ₇ CH.

9. Tris [4- (1H, 1H, 2H, 2H-perfluorodecyl) phenyl] phosphite.

10. Tris [2- (1H, 1H, 2H, 2H-perfluorodecyl) phenyl] phosphite.

11. Tris [2,4-bis (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl] phosphite.

12. Tris [3- (1H, 1H, 2H, 2H-perfluorodecyl) -5-chlorophenyl] phosphite.

13. Catalyst comprising a transition metal and at least one tris [(1 H, 1 H, 2H, 2H-perfluoroalkyl) phenyl] phosphite of formula (I).

14. Catalyst according to claim 13, characterized in that the transition metal is rhodium, palladium, ruthenium, nickel, iridium, chromium, cobalt or iron.

15. Catalyst according to claim 13 or 14, characterized in that the transition metal is rhodium and that the phosphite of formula (I) is tris [4- (1 H, 1 H, 2H, 2H-perfluorodecyl) phenyl ]phosphite.

16. Use of a catalyst according to any one of claims 13 to 15 for carrying out chemical reactions in biphasic catalysis with a fluorinated phase.

17. Use according to claim 16, characterized in that the chemical reaction is a hydroformylation reaction.