EP1150987A1 - Tris((1h,1h, 2h,2h-perfluoroalkyl)aryl)phosphite und ihre anwendungen in katalyse - Google Patents

Tris((1h,1h, 2h,2h-perfluoroalkyl)aryl)phosphite und ihre anwendungen in katalyse

Info

Publication number
EP1150987A1
EP1150987A1 EP00903765A EP00903765A EP1150987A1 EP 1150987 A1 EP1150987 A1 EP 1150987A1 EP 00903765 A EP00903765 A EP 00903765A EP 00903765 A EP00903765 A EP 00903765A EP 1150987 A1 EP1150987 A1 EP 1150987A1
Authority
EP
European Patent Office
Prior art keywords
tris
formula
perfluoroalkyl
phosphite
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00903765A
Other languages
English (en)
French (fr)
Inventor
Jean-Luc Couturier
Thomas Mathivet
Eric Monflier
Yves Castanet
André Mortreux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP1150987A1 publication Critical patent/EP1150987A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

Definitions

  • 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.
  • the fluorinated phase is a solvent rich in C-F bonds (fluorocarbons, hydrofluorocarbons).
  • the system 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,
  • 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.
  • the catalyst is easily recovered by cooling the reaction medium to a temperature below the miscibility temperature of the two phases.
  • 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.
  • spacers non-fluorinated groups
  • CH2 polymethylene radicals
  • n n ranging from 1 to 3
  • phenylene radical -CeH - n ranging from 1 to 3
  • 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.
  • 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.
  • 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%.
  • 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 + ⁇ 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)
  • 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)
  • step b) 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.
  • X represents a bromine atom.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • MS mass spectrometry
  • 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.
  • R H or CH 3 -
  • Rf CF 3 (CF 2 ) 7 C 2 H 4 -.
  • 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.
  • 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.
  • 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.
  • Example 4 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
  • 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.
  • 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 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.
  • 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.
  • RMN 19 F ⁇ 1 H ⁇ (diethyl ether, external lock on CDCI 3 ) ⁇ (ppm): -81, 06 (18F, t, 3 J FF 9.3 Hz, 6 x -CF 3 ), -114.92 (6F, um, 3 x -CF - in ⁇ of 4-C arom), - 115.15 (6F, um, 3 x -CF 2 - in ⁇ 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 -).
  • 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.
  • 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 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP00903765A 1999-02-10 2000-02-09 Tris((1h,1h, 2h,2h-perfluoroalkyl)aryl)phosphite und ihre anwendungen in katalyse Withdrawn EP1150987A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9901552A FR2789391B1 (fr) 1999-02-10 1999-02-10 Procede de preparation de tris((1h,1h,2h,2h-perfluoroalkyl) aryl) phosphites, lesdits arylphosphites fluores et leurs applications en catalyse biphasique a phase fluoree
FR9901552 1999-02-10
PCT/FR2000/000310 WO2000047590A1 (fr) 1999-02-10 2000-02-09 Tris [(1h,1h, 2h,2h-perfluoroalkyl) aryl]phosphites et leurs applications en catalyse

Publications (1)

Publication Number Publication Date
EP1150987A1 true EP1150987A1 (de) 2001-11-07

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EP00903765A Withdrawn EP1150987A1 (de) 1999-02-10 2000-02-09 Tris((1h,1h, 2h,2h-perfluoroalkyl)aryl)phosphite und ihre anwendungen in katalyse

Country Status (4)

Country Link
US (1) US6534684B1 (de)
EP (1) EP1150987A1 (de)
FR (1) FR2789391B1 (de)
WO (1) WO2000047590A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001051441A1 (en) * 2000-01-12 2001-07-19 Eastman Chemical Company Hydroformylation method for making aldehydes from sterically hindered olefins

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZW9882A1 (en) * 1981-11-03 1983-02-02 Mineral Tech Council Selective solvent extraction using organophosphorus and carboxylic acids
US5463082A (en) * 1993-07-08 1995-10-31 Exxon Research And Engineering Company Fluorous multiphase systems
DE19702025A1 (de) * 1997-01-23 1998-07-30 Studiengesellschaft Kohle Mbh Verwendung perfluoralkylsubstituierter Phosphorverbindungen als Liganden für die homogene Katalyse in überkritischem Kohlendioxid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0047590A1 *

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Publication number Publication date
US6534684B1 (en) 2003-03-18
FR2789391B1 (fr) 2003-06-27
WO2000047590A1 (fr) 2000-08-17
FR2789391A1 (fr) 2000-08-11

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