WO2015000543A1 - Rare earth metal-bis(perfluoroalkyl)phosphinates as lewis acid catalysts - Google Patents

Abstract

The invention relates to rare earth metal-bis(perfluoroalkyl) phosphinates as Lewis acid catalysyts, to special compounds and to the method for the production thereof.

Description

 Rare earth bis (perfluoroalkyl) phosphinates as Lewis acid

 catalysts

The invention relates to rare earth bis (perfluoroalkyl) phosphinates as Lewis acid catalysts, to specific compounds and to their processes for the preparation.

Lewis acid catalysis is a widely used methodology in organic synthesis and of outstanding importance for the industrial production of various substances. Among the many important industrial processes catalyzed by Lewis acids include Friedel-Crafts alkylations and acylations of aromatics, Gattermann-Koch reactions, Beckmann and Fries rearrangements, Mukaiyama-aldol condensations. [Acid Catalysis in Modern Organic Synthesis, H. Yamamoto and K. Ishihara (Eds.), Wiley-VCH, Weinheim, 2008].

G.N. Lewis defines an acid as a substance known as

Electron pair acceptor can act. According to this definition, Lewis acids are electron deficient molecules or species. The commonly used Lewis acidic catalysts such as AICI ₃ , TiCl ₄ , ZnCl ₂ and BF ₃ - Diethyletherat are sensitive to moisture and can not be recovered usually after completion of the reaction. Other known Lewis acids are rare earth perfluoroalkanesulfonates, in particular rare earth trifluoromethanesulfonates (triflates) [S. Kobayashi, M. Sugiura, H. Kitagawa, WW-L. Lam, Chem. Rev. 2002, 102, p. 2227-2302; S. Kobayashi, Eur. J. Org. Chem. 1999, p. 5-27]. Such Lewis acids can be found in

catalytic amount can be used in the desired reactions and can be reused usually after the desired conversion without loss of activity. However, the hydrolytic stability of the water-soluble rare earth metal triflates can lead to pollution of waste water with these chemicals, which can pollute the environment over a longer period of time. There is therefore still a need for economically attractive alternative Lewis acid catalysts, so that the Lewis acid-catalyzed reactions can be optimally carried out.

The object of the present invention is therefore to develop alternative Lewis acid catalysts which allow a reaction of the desired catalyzed reactions in good yield, which can be ideally worked up without losing their activity, and are less polluting than the previously known Lewis Acid catalysts.

Surprisingly, it was found that the combination of

Rare earth metal cations and bis (perfluoroalkyl) phosphinate anions allow the development of new catalysts that are as catalytically active as the known catalysts with perfluoroalkanesulfonate anions, but can be degraded faster in nature. In some cases, the rare earth bis (perfluoroalkyl) phosphinates even show higher catalytic activity than the rare earth metal compounds

Perfluoroalkanesulfonate anions or they allow another

Isomer distribution in the final process product.

Single rare earth bis (perfluoroalkyl) phosphinates are heretofore known.

SU 589756 describes the compounds Nd [(C ₃ F ₇ ) ₂ P (O) O] 3 and EU [(A7-C ₄ F ₉ ) ₂ P (O) O] ₃ .

In US 6538805 composite materials for signal-emitting

Devices described with rare earth metal compounds are. In Example 1, for example, a material of the formula

{ErYb [OOP (C ₈ F ₁₇ ) 2] 3} n.

WO 03/018592 discloses a composition comprising

Rare earth metal and a ligand system described. Claim 6 lists the complexes Er [(nC ₈ F ₁₇ ) ₂ POO] ₃ , ErYb [(nC ₈ F ₁₇ ) ₂ POO] ₆ , ErYb ₄ [(nC ₈ F ₁₇ ) ₂ POO] ₁₅ , ErYb [( r7-C ₆ F _{13) 2} POO] _6, eryB [(A7-C ₄ F _{9) 2} POO] _6,

ErYb ₃ [((CF ₃ ) ₂ CF (CF ₂ ) ₆ ) ₂ POO] ₁₂ , ErYb ₃ [(r 7 -C ₁₀ F ₂₃ ) ₂ POO] ₁₂ , ErYb ₃ [(nC ₈ F ₁₇ ) (A7 -C ₁₀ F ₂₃ ) POO] ₁₂ , ErYb [(A7-C ₈ F ₁₇ ) ₂ POO] ₆ and ErYb ₁₀ [(nC ₈ F ₁₇ ) ₂ POO] ₃₃ .

Prior art applications of the specific rare earth compounds as described above are in the field of surfactants or in the field of optical devices such as optical waveguides or in optical amplification media.

The object of the invention is therefore the use of at least one compound of the formula I.

[RE] ^{Z +} z [(R _f ) ₂ P (O) O] - I,

where RE is a rare earth metal,

z corresponds to the charge of the rare earth metal cation and

R, / ^{'so-nonafluorobutyl} group, sec-nonafluorobutyl or terr.-nonafluorobutyl means _f each independently represent trifluoromethyl, pentafluoroethyl, heptafluoropropyl, iso-, n-heptafluoropropyl, n-nonafluorobutyl,

as a Lewis acid catalyst.

In a preferred embodiment of the invention, the

Rare earth metal RE preferably selected from the group consisting of Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.

The object of the invention is therefore also the use of at least one compound of the formula I as described above, wherein the rare earth metal is selected from the group Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.

As is known, rare earth cations can have a valence of 2, 3 or 4 (z = 2, 3 or 4). Preference is given to the value of

corresponding cation 3 (z = 3).

The object of the invention is therefore furthermore the use of at least one compound of the formula I as described above and preferably where z is 2, 3 or 4.

The object of the invention is therefore furthermore the use of at least one compound of the formula I as described above and preferably where z is 3.

The catalytic activity of Sc ³⁺ , Y ³⁺ and lanthanide ³⁺ ions as Lewis acids depends on the ionic radius of these metal cations [C.

Eischenbroich, Organometallchemie, 6th edition, BG Teubner Verlag, Wiesbaden, 2008]. The cations with the smallest ionic radii, Sc ³⁺ , Y ³⁺ , Yb ³⁺ and Lu ³⁺ , have a high electron affinity and are therefore of particular interest from a catalysis standpoint.

In a particularly preferred embodiment of the invention, the rare earth metals of the formula I are selected from Sc, Y, Yb and Lu.

The object of the invention is therefore furthermore the use of at least one compound of the formula I as described above, wherein the rare earth metal is selected from the group Sc, Y, Yb and Lu. The substituent R _f in the compounds of formula I are each independently trifluoromethyl, pentafluoroethyl, / ^{'so-heptafluoropropyl,} /? - Heptafluoropropyl, n-nonafluorobutyl, / ^{'so-nonafluorobutyl} or tert-nonafluorobutyl.

 In a preferred embodiment of the invention, as before

described, the two substituents R _{f are the} same.

In a preferred embodiment of the invention, as before

each R _f is independently preferred

Pentafluoroethyl or n-nonafluorobutyl.

In a particularly preferred embodiment of the invention, as described above, R _{f is in} each case identical and is pentafluoroethyl or n-nonafluorobutyl.

In a most preferred embodiment of the invention as described above, R _{f is} pentafluoroethyl.

Another object of the invention are the compounds of formula II

[RE] ^{Z +} z [(C ₂ F ₅ ) ₂ P (0) 0] - II,

wherein RE represents a rare earth metal selected from Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and

z corresponds to the charge of the rare earth metal cation.

In compounds of the formula II, z is preferably 2, 3 or 4.

In compounds of the formula II, z is particularly preferably 3.

Another object of the invention are therefore the compounds of formula II, as described above, wherein z is 2, 3 or 4.

Another object of the invention are therefore the compounds of formula II, as described above, wherein z is 3. The formula II can be used in this case in the following notation: RE [(C ₂ F ₅ ) ₂ POO] ₃ , where RE is Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.

Another object of the invention are the compounds of formula III

[RE] ^{z +} z [(A7-C ₄ F _{9) 2} P (O) O] - III,

wherein RE represents a rare earth metal selected from Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho and Tm and

z corresponds to the charge of the rare earth metal cation.

In compounds of the formula III, z is preferably 2, 3 or 4.

In compounds of the formula III, z is particularly preferably 3.

Another object of the invention are therefore the compounds of formula III, as described above, wherein z is 2, 3 or 4.

Another object of the invention are therefore the compounds of formula III, as described above, wherein z is 3. Formula III can be used in this case in the following notation:

RE [(nC ₄ F ₉ ) ₂ POO] ₃ , where RE is Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho and Tm.

As previously described in use, so are the

Compounds of formula II and formula III particularly preferred Lewis acid catalysts.

Very particularly preferred Lewis acid catalysts are the

Compounds of the formula II as described above and described as being preferred.

The compounds of formula I, II and / or III can be prepared based on known synthetic methods, such as in SU 589756 described. Details in this regard are given in the examples and are generally valid.

In general, the corresponding bis (perfluoroalkyl) phosphinic acid with the rare earth metal or with an oxide or carbonate of the

 Rare earth metal reacted in a suitable solvent.

Suitable solvents are, for example, water or alcohols. A suitable alcohol is, for example, methanol. Preferably, water is used as the solvent.

 The reaction temperature is preferably between 0 ° C and 150 ° C, more preferably between 25 ° C and 120 ° C, very particularly

preferably between 60 ° C and 100 ° C. The rare earth metals can be found in any existing form of

 Metal particles are used, for example in the form of powders or chips. The acid used in the reaction is strong enough to open up even more massive metal particles such as chips. Since the compounds of the formulas II and III, as described above, are not known in the prior art, a further subject of the invention is a process for preparing compounds of the formula II or III, as described above or described as being preferred

in that bis (pentafluoroethyl) phosphinic acid or bis (n-nonafluorobutyl) phosphinic acid with an oxide or carbonate of the

Rare earth metal RE or with the rare earth element RE is reacted as such, wherein the rare earth element RE is selected as indicated in formula II or formula III. Another object of the invention is a Lewis acid catalyst as described above or described as preferred for use in a Lewis acid catalyzed reaction. In a preferred embodiment of the invention, the Lewis acid-catalyzed reaction is selected from a condensation reaction, alcoholysis, aldol reaction, Mukaiyama-aldol reaction, Gattermann-Koch reaction, Beckmann and Fries rearrangement, Friedel-Crafts acylation, Friedel-Crafts alkylation, Mannich reaction, Diels-Alder reaction, Aza-Diels-Alder reaction, Baylis-Hillman reaction, Reformatsky reaction, Claisen rearrangement, Prins cyclization reaction, allylation of carbonyl compounds, cyanation of aldehydes and ketones, 1, 3-dipolar cycloaddition or Michael reaction.

Due to the specific solution properties of the compounds of formula I as described above or described as preferred, the choice of solvent for the Lewis acid catalyzed reaction is

crucial.

Suitable protic solvents when using the

Lewis acid catalysts according to the invention are ethanol or

Methanol. Suitable aprotic solvents when using the

Lewis acid catalysts according to the invention are acetonitrile and 1, 2-dichloroethane.

The class of ionic liquids are also suitable as solvents when using the Lewis acid catalysts according to the invention.

An ionic liquid is understood as meaning salts which as a rule consist of an organic cation and an inorganic anion. They contain no neutral molecules and usually have melting points of less than 373 K [Wasserscheid P, Keim W, 2000, Angew. Chem. 1 12: 3926]. Due to their salt character, ionic liquids have unique material properties, such as a low one Vapor pressure, a liquid state over a wide

Temperature range, are not flammable, show high electrical conductivity and high electrochemical and thermal stability. Suitable ionic liquids as solvents when using the Lewis acid catalysts of the invention are ionic

Liquids that have an organic cation and their anion

is selected from the group Cl ^~, Br ^~ [RiCOO] ^~, [RIS0 _3] ^~, [R ₂ COO] ^~ [R2SO3] -, [R1OSO3] - [BF _4] ^~ [SO _4] ² - [HSO4] ¹ -, [(R ₁ ) ₂ P (O) O] - _l ^ Ρ (Ο) Ο ₂ ] ² -, [(RiO) ₂ P (0) 0] -, [(RiO) P (O) O _2] ² -, [(R _{2) 2} P (0) 0] -, [R ₂ P (0) 0 _2] ² -,

[(FSO ₂ ) ₂ N] -, [(R ₂ S0 ₂ ) ₂ N] - [(R ₂ S0 ₂ ) ₃ C] - [(FSO ₂ ) ₃ C] -, [P (R ₂ ) _y F _6-y ] ^"

-, [B(R₂)F₂(CN)]- oder [BF _X (R ₂ ) _4-X ] -, [BF _X (CN) _4-X ] -,

-, [B (R ₂ ) F ₂ (CN)] - or

[B (R ₂ ) F (CN) ₂ ] - where R 1 is independently of one another H and / or a linear or branched alkyl group having 1 to 12 C atoms,

R ₂ each, independently of one another, denotes a partially fluorinated or perfluorinated linear or branched alkyl group having 1 to 12 C atoms or pentafluorophenyl,

x is the integer 0, 1, 2 or 3,

y is the integer 0, 1, 2, 3 or 4 and

a is the integer 1 or 2.

A perfluorinated linear or branched alkyl group having 1 to 4 C atoms is, for example, trifluoromethyl, pentafluoroethyl, n-heptafluoropropyl, iso-heptafluoropropyl, n-nonafluorobutyl, sec-nonafluorobutyl or tert-butyl

Nonafluorobutyl. By analogy, R ₂ defines a linear or branched perfluorinated alkyl group having 1 to 12 C atoms, comprising the abovementioned perfluoroalkyl groups and, for example, perfluorinated n-hexyl, perfluorinated n-heptyl, perfluorinated n-octyl, perfluorinated ethylhexyl, perfluorinated n-nonyl, perfluorinated n-decyl, perfluorinated n-undecyl or perfluorinated n-dodecyl. Preferably, R ₂ is trifluoromethyl, pentafluoroethyl or nonafluorobutyl, very particularly preferably trifluoromethyl or pentafluoroethyl.

The variable y is preferably 1, 2 or 3, more preferably 3.

Preferred solvents are ionic liquids with the anions

[P (R ₂ ) y 6 y] - and [R ₂ SO 3] ^" where R ₂ and y have the meanings given above or are preferably given in. Particularly preferred solvents are ionic liquids having the anions [P (C ₂ F ₅ ) 3F ₃ r and [CF3SO3] ^" .

The organic cations are generally not limited and are preferably selected from imidazolium cations, pyridinium cations or pyrrolidinium cations, which may be substituted accordingly, as known in the art.

Very particular preference is given to the ionic liquids 1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate {[EMIM] [FAP]} or 1-ethyl-3-methylimidazolium trifluoromethanesulfonate {[EMIM] [CF ₃ SO ₃ ] } selected as the solvent.

The following examples of Lewis acid catalyzed reactions show that the use of the compounds of the formula I as described above or described as preferred, in direct comparison with

Rare earth metal perfluoroalkanesulfonates also very good yields with short reaction times can be achieved.

The suitability of the compounds of formula I as Lewis acid catalysts is evidenced by a condensation reaction, an alcoholysis, a ukaiyama-aldol reaction, a Friedel-Crafts alkylation, a Friedel-Crafts acylation, a Diels-Alder reaction, an Aza-Diels-Alder Reaction and a Michael reaction. These reaction types are

representative of Lewis acid catalyzed reactions.

Examples:

The resulting materials are characterized by X-ray fluorescence analysis, elemental analysis and NMR spectroscopy. The NMR spectra are measured on solutions on a Bruker Avance III 400 MHz spectrometer. The measurement frequencies of the various cores are: ¹ H: 400.13 MHz, ¹⁹ F: 376.49 MHz, ³ P: 161, 97 MHz and ¹³ C: 100.61 MHz. Referencing is done with external reference: TMS for H and ¹³ C spectra; CCI ₃ F - for ¹⁹ F and H ₃ P0 ₄ - for ³ P spectra. The solvents used are indicated separately.

X-ray fluorescence analysis measurements are performed on a

X-ray fluorescence spectrometer of the Eagle II μ-Probe from the company Röntgenanalytik Messtechnik GmbH (Taunusstein, Germany)

carried out. The measurements use a nitrogen-cooled silicon-lithium detector from EDAX (Mahwah, USA). Through a monocapillary, the stimulating radiation of the rhodium tube is directed to the sample to allow a punctual radiation.

To determine the carbon, hydrogen and / or nitrogen content, combustion analyzes are carried out with the Elementar-Analyzer Euro EA 240 from Perkin-Elmer using the Callidus software. Sulfanilamide is used as the calibration substance. For sample weighing, an electronic microbalance (Sartorius M2P) is used. The

weighed amounts of substance are 0.5 - 3 mg.

Example 1. Preparation of scandium (III) tris [bis (pentafluoroethyl) phosphinate], Sc [(C ₂ F ₅ ) ₂ P (O) O] 3

2 Sc 6 + (C ₂ F _{5) 2} P (0) OH 2 Sc [(C ₂ F5) ₂ P (0) 0] 3 + 3 H ₂ f In a 100 ml round bottom flask 0.098 g (2.18 mmol) of scandium chips are presented with 20 ml of water. To this are added 1.54 g (5.10 mmol)

Bis (pentafluoroethyl) phosphinic acid, (C ₂ F _{5) 2} P (0) OH, dropwise

added. At the same time a gas evolution is observed. The

Reaction mixture is heated to 70 ° C for 3 hours. unresolved

Scandium chips are filtered off and the reaction solution is concentrated to dryness. The remaining solid is dried for 20 hours at 100 ° C and 80 hPa. 1:38 g (1:46 mmol) of scandium (III) - tris [bis (pentafluoroethyl) phosphinate], Sc [(C ₂ F5) ₂ P02] 3 are isolated as a white, finely powdered solid. Yield: 85.9%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F , p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _{P, F} = 76 Hz.

X-ray fluorescence analysis

 Theoretical: Sc (25 at.%), P (75 at.%).

 Experimental: Sc (25.1 at.%), P (74.4 at.%).

Elemental analysis Ci ₂ F ₃₀ O ₆ P3

Theoretically,%: C 15.20.

Experimental,%: C 15.09.

Example 2. Preparation of yttrium (III) tris [bis (pentafluoroethyl) phosphinate], Y [(C ₂ F ₅ ) ₂ P (0) 0] ₃

Y ₂ 0 ₃ + 6 (C ₂ F ₅ ) ₂ P (0) OH- ^ 2 Y [(C ₂ F ₅ ) ₂ P (0) 0] ₃ + 3 H ₂ 0

In a 100 ml round bottom flask, 0.50 g (2.21 mmol) of yttrium (III) oxide, Y ₂ O ₃ , are suspended in 15 ml of water. 4.03 g (13.33 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH, are added dropwise to the suspension. The reaction mixture is heated to 80 ° C for 1.5 hours heated. Undissolved yttrium (III) oxide is filtered off and the

Reaction solution at 50 ° C concentrated to dryness. The remaining solid is dried for 24 hours at 100 ° C and 80 hPa. 3.74 g (3.77 mmol) of yttrium (III) tris [bis (pentafluoroethyl) phosphinate], Y [(C ₂ F ₅ ) 2PO 2] 3, can be isolated as a white, finely powdered solid. Yield: 86.1%.

¹⁹ F-NMR (solvent: CD ₃ OD), δ, ppm: -82.1 s (CF ₃ ), -126.1 d (CF ₂ ), ² J _F , p = 76 Hz.

3 P-NMR (solvent: CD ₃ OD), δ, ppm: 0.1 quin, ² J _P , _F = 76 Hz.

X-ray fluorescence analysis

 Theoretical: Y (25 atomic%), P (75 atomic%).

 Experimental: Y (23 at%), P (77 at%).

Elemental Analysis C ₁₂ F ₃ oO6P3Y:

Theoretical%: C 14.53.

Experimental%: C 14.18. Example 3. Preparation of Lanthanum (III) tris [bis (pentafluoroethyl) phosphinate], La [(C ₂ F ₅ ) ₂ P (0) 0] ₃

La ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH * - 2 La [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0 in a 100 ml round bottom flask 0:54 g (1.65 mmol) lanthanum (III) oxide,

La ₂ 0 ₃ , suspended in 15 ml of water. 3.07 g (10.16 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (O) OH, are added dropwise to the suspension. The reaction mixture is heated to 80 ° C for 1.5 hours. Undissolved lanthanum (III) oxide is filtered off and the

Reaction solution is concentrated at 50 ° C to dryness. Of the

remaining solid is dried for 24 hours at 100 ° C and 80 hPa. 3.27 g (3.14 mmol) of lanthanum (III) tris [bis (pentafluoroethyl) phosphinate], La [(C ₂ F ₅ ) ₂ P0 ₂ ] 3 can be isolated as a white, finely powdered solid. Yield: 95.1%. 9F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F , p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _P , _F = 76 Hz.

X-ray fluorescence analysis

Theoretically: La (25 atomic%), P (75 atomic%).

Experimental: La (26.8 at%), P (73.2 at%).

Elemental Analysis Ci ₂ F ₃₀ LaO6P3:

Theoretical%: C 13.83.

Experimental%: C 13.82.

Example 4. Preparation of cerium (III) tris [bis (pentafluoroethyl) phosphinate], Ce [(C ₂ F ₅ ) ₂ P (O) O] ₃

Ce ₂ (CO ₃ ) 3 - H ₂ O + 6 (C ₂ F ₅ ) ₂ P (0) OH- -2 Ce [(C ₂ F ₅ ) ₂ P (O) O] ₃ + 4 H ₂ O + 3 C0 ₂ f In a 50 ml round bottom flask, 0.298 g (0.647 mmol) cerium (III) carbonate monohydrate, 0β ₂ (0Ο ₃ ) ₃ · H ₂ O, are suspended in 14.90 g water and 0.953 g (3.155 mmol) bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH, are added dropwise. The reaction solution is stirred for 20 hours at RT and undissolved cerium (III) carbonate hydrate filtered off. The filtrate is concentrated at 50 ° C (oil bath temperature) and 0.1 Pa to dryness and dried for 4 hours. 1080 g (1.035 mmol) of cerium (III) tris [bis (pentafluoroethyl) phosphinate], Ce [(C ₂ F ₅ ) ₂ PO ₂ ] ₃ , can be isolated as a white, finely powdered solid. Yield: 98.4%. ¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _{F, P} = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _{P, F} = 76 Hz. X-ray fluorescence analysis

 Theoretically: Ce (25 at.%), P (75 at.%).

 Experimental: Ce (31.85 at.%), P (68.1 at.%).

Elemental analysis C ₁₂ CeF ₃ oO 6 P ₃ :

Theoretical%: C 13.82.

Experimental%: C 13.81. Example 5. Preparation of praseodymium (III) tris [bis (pentafluoroethyl) phosphinate], Pr [(C ₂ F ₅ ) 2P (0) 0] ₃

Pr ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH - - 2 Pr [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0

0.38 g (1.15 mmol) of praseodymium (III) oxide, Pr ₂ O ₃ , are suspended in 20 ml of water in a 50 ml round bottom flask. To the suspension are added 2.08 g (6.89 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH,

added dropwise. The reaction mixture is heated at 100 ° C for 3 hours. Undissolved praseodymium (III) oxide is filtered off and the reaction solution at 50 ° C is concentrated to dryness. Of the

resulting solid is dried for 20 hours at 100 ° C at 80 hPa. 2.35 g (2.25 mmol) of praseodymium (III) tris [bis (pentafluoroethyl) phosphinate], Pr [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ , can be isolated as a greenish, finely powdered solid. Yield: 97.8%. ¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F, p = 76 Hz.

³ P-NMR (solvent: D ₂ 0), δ ppm: 3.5 quin, ² J _{P> F} = 76 Hz.

X-ray fluorescence analysis

 Theoretically: Pr (25 at.%), P (75 at.%).

Experimental: Pr (30.1 atom%), P (69.9 atom%). Elemental analysis Ci2F ₃ o0 ₆ P3 r:

Theoretical%: C 13.81.

Experimental%: C 13.85.

Example 6. Preparation of neodymium (III) tris [bis (pentafluoroethyl) phosphinate], Nd [(C ₂ F ₅ ) ₂ P (0) 0] 3

Nd ₂ 0 ₃ + 6 (C ₂ F ₅ ) ₂ P (0) OH- 2 Nd [(C ₂ F ₅ ) ₂ P (0) 0] 3 + 3 H ₂ 0

0.266 g (0.791 mmol) of neodymium (III) oxide, Nd ₂ O ₃ , are suspended in 10 ml of water in a 50 ml round bottom flask. 1.038 g (3.437 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (O) OH, are added to this suspension.

added dropwise. The reaction mixture is heated at 60 ° C (oil bath temperature) for 4 hours. Undissolved neodymium (III) oxide is filtered off and the reaction solution is heated at 40 ° C. and 0.1 Pa until

Evaporated to dryness. The resulting solid is dried for 4 hours. 1,182 g (1,128 mmol) of neodymium (III) tris [bis (pentafluoroethyl) phosphinate], Nd [(C ₂ F ₅ ) ₂ PO ₂ ] 3, can be isolated as a lilac-colored, finely powdered solid. Yield: 98.5%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _FP = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0; δ in ppm): 3.5 (quin, ² J _{P, F} = 76 Hz).

X-ray fluorescence analysis

 Theoretical: Nd (25 at.%), P (75 at.%).

 Experimental: Nd (30.9 at%), P (69.1 at%).

Elemental Analysis C ₂ F ₃₀ NdO ₆ P 3:

Theoretical%: C 13.76.

Experimental%: C 13.53. Example 7. Preparation of Samarium (III) tris [bis (pentafluoroethyl) phosphinate], Sm [(C ₂ F ₅ ) ₂ P (0) 0] 3

Sm ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH "- 2 Sm [(C ₂ F5) ₂ P (0) 0] 3 + 3 H ₂ 0

In a 50 ml round bottom flask, 0.30 g (0.86 mmol) of samarium (III) oxide, Sm ₂ O ₃ , are suspended in 10 ml of water. 1.60 g (5.30 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F 5) ₂ P (O) OH, are added dropwise to the suspension. The reaction mixture is heated with stirring to 80 ° C for 3 hours. Undissolved samarium (III) oxide is filtered off and the reaction solution is concentrated to dryness at 50 ° C. Of the

remaining solid is dried for 24 hours at 100 ° C and 80 hPa. 1.74 g (1.65 mmol) of samarium (III) tris [bis (pentafluoroethyl) phosphinate], Sm [(C ₂ F ₅ ) ₂ P0 ₂ ] 3, can be isolated as a white, finely powdered solid. Yield: 93.4%. 9F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F , p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _{P, F} = 76 Hz.

X-ray fluorescence analysis

 Theoretically: Sm (25 atomic%), P (75 atomic%).

 Experimental: Sm (25.3 at.%), P (74.7 at.%).

Elemental analysis C ₁₂ F3 ₀ O ₆ P ₃ Sm:

Theoretical (%): C (13.68).

Experimental (%): C (13.63).

Example 8. Preparation of europium (III) tris [bis (pentafluoroethyl) phosphinate], Eu [(C ₂ F ₅ ) ₂ P (O) O] ₃

Eu ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH * - 2 Eu [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0 In a 50 ml round-bottomed flask 0.25g (0.71 mmol) of europium (III) oxide, Eu suspended in 10 ml of water ₂ 0 _3>. To the suspension are added 1.14 g (3.77 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F 5) ₂ P (O) OH,

added dropwise. The reaction mixture is heated with stirring to 80 ° C for 3 hours. Undissolved europium (III) oxide is filtered off and the reaction solution is concentrated at 50 ° C to dryness. The remaining solid is dried for 20 hours at 100 ° C and 80 hPa. 1.21 g (1.15 mmol) of europium (III) tris [bis (pentafluoroethyl) phosphinate], Eu [(C ₂ F ₅ ) ₂ P0 ₂ ] 3, can be isolated as a white, finely powdered solid. Yield: 91.3%. 9F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F, p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _PF = 76 Hz.

X-ray fluorescence analysis

 Theoretically: Eu (25 atomic%), P (75 atomic%).

Experimental: Eu (23.1 at%), P (74.4 at%). Elemental Analysis C ₁₂ EuF ₃₀ O6P3:

Theoretical%: C 13.66.

Experimental%: C 13.10.

Example 9. Preparation of Gadolinium (III) tris [bis (pentafluoroethyl) phosphinate], Gd [(C ₂ F ₅ ) ₂ P (O) O] ₃

Gd ₂ (C0 ₃ ) ₃ - H ₂ 0 + 6 (C ₂ F ₅ ) ₂ P (0) OH -2 Gd [(C ₂ F ₅ ) ₂ P (0) 0] 3 + 4 H ₂ O + 3 C0 ₂ f

In a 25 ml round bottom flask 0.401 g (0.811 mmol) of gadolinium (lll) - carbonate monohydrate, Gd ₂ (CO _{3) 3} ^»H ₂ O, suspended in 14.90 g of water and

1.058 g (3.503 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F _{5) 2} P (O) OH, are added dropwise. The reaction solution is allowed to stand for 20 hours RT stirred and undissolved gadolinium (III) carbonate hydrate filtered off. The filtrate is concentrated at 40 ° C (oil bath temperature) and 0.1 Pa to dryness and dried for 6 hours. 1.209 g (1.14 mmol) of gadolinium (III) tris [bis (pentafluoroethyl) phosphinate], Gd [(C ₂ F 5) ₂ PO ₂ ] 3, can be isolated as a white, finely powdered solid. Yield: 97.6%. (By

Ion chromatography, a carbonate content of 0.12% can be determined). 9F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F , p = 74 Hz.

³ P-NMR (solvent: D ₂ 0), δ, ppm: 2.95 m.

X-ray fluorescence analysis

Theoretically: Gd (25 at%), P (75 at%).

Experimental: Gd (32.4 at.%), P (67.6 at.%).

Elemental analysis Ci ₂ F ₃ oGd0 ₆ P3:

Theoretical%: C 13.59.

Experimental%: C 12.99.

Notes on X-ray fluorescence analysis to Ce (Example 4), Gd and Nd (Example 6):

 The high deviations compared to the ideal ratio are due to the sample preparation. To protect the device and the detector, the samples are covered with a special foil.

Example 10. Preparation of Terbium (III) tris [bis (pentafluoroethyl) phosphinate], Tb [(C ₂ F ₅ ) ₂ P (O) O] ₃

Tb ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH - 2 Tb [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0

0.20 g (0.55 mmol) of terbium (III) oxide, Tb ₂ O ₃ , are suspended in 10 ml of water in a 50 ml round bottom flask. To the suspension, 1.00 g (3.31 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (O) OH, is added dropwise added. The reaction mixture is heated to 100 ° C with stirring for 3.5 hours. Undissolved constituents are filtered off and the

Reaction solution is concentrated at 50 ° C to dryness. Of the

remaining solid is dried for 20 hours at 100 ° C and 80 hPa. 1.07 g (1.01 mmol) terbium (III) tris [bis (pentafluoroethyl) phosphinate],

Tb [(C ₂ F 5) ₂ P0 ₂ ] 3 can be isolated as a white, finely powdered solid. Yield: 92.1%.

¹⁹ F-NMR (solvent: D ₂ O), δ, ppm: -80.9 s (CF _3), -125.9 d (CF ₂₎ ² J _{F, P} = 76 Hz.

³ P-NMR (solvent: D ₂ O), δ, ppm: 2.68 quin, ² J _PF = 76 Hz).

X-ray fluorescence analysis

Theoretical: Tb (25 at.%), P (75 at.%).

Experimental: Tb (21.6 at.%), P (78.4 at.%).

Elemental Analysis Ci ₂ F ₃₀ O ₆ P ₃ Tb:

Theoretical%: C 13.57.

Experimental%: C 13.31.

Example 11. Preparation of dysprosium (III) tris [bis (pentafluoroethyl) phosphinate], Dy [(C ₂ F ₅ ) ₂ P (0) 0] ₃

Dy ₂ 0 ₃ + 6 (C ₂ F ₅ ) ₂ P (0) OH- ^ 2 Dy [(C ₂ F ₅ ) ₂ P (0) 0] ₃ + 3 H ₂ 0 In a 50 ml round bottom flask, add 1.00 g (2.68 mmol) dysprosium (III) oxide, Dy ₂ 0 ₃ , suspended in 25 ml of water. 3.62 g (11.98 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (O) OH, are added dropwise to the suspension. The reaction mixture is heated to 100 ° C with stirring for 3 hours. Undissolved dysprosium (III) oxide is filtered off and the reaction solution is concentrated at 50 ° C to dryness. The remaining solid is dried for 24 hours at 100 ° C and 80 hPa. 3.73 g (3.50 mmol) dysprosium (III) tris [bis (pentafluoroethyl) phosphinate], Dy [(C ₂ F ₅ ) 2PO 2] 3 can be isolated as a white, finely powdered solid. Yield: 87.6%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.7 s (CF ₃ ), -125.8 d (CF ₂ ), ² J _F , p = 76 Hz.

³ P-NMR (solvent: D ₂ 0), δ, ppm: 2.68 quin, ² J _P , _F = 76 Hz.

X-ray fluorescence analysis

Theoretical: Dy (25 at.%), P (75 at.%).

Experimental: Dy (26.9 at%), P (73.1 at%).

Elemental analysis Ci ₂ DyF ₃ o0 ₆ P3:

Theoretical%: C 13.53.

Experimental%: C 13.23.

Example 12. Preparation of holmium (III) tris [bis (pentafluoroethyl) phosphinate], Ho [(C ₂ F ₅ ) ₂ P (0) 0] ₃

Ho ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH 2 HO [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0

In a 50 ml round bottom flask, 0.25 g (0.66 mmol) holmium (III) oxide,

Ho ₂ 0 ₃ , suspended in 10 ml of water. To the suspension are added 1.19 g (3.94 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH,

added dropwise. The reaction mixture is heated to 70 ° C with stirring for 3 hours. Undissolved holmium (III) oxide is filtered off and the reaction solution is concentrated at 50 ° C to dryness. The resulting solid is dried for 20 hours at 100 ° C and 80 hPa. 1.37 g (1.28 mmol) of holmium (III) tris [bis (pentafluoroethyl) phosphinate], Ho [(C ₂ F ₅ ) ₂ P0 ₂ ] 3, can be isolated as a white, finely powdered solid. Yield: 97.5%. 9F-NMR (solvent: D ₂ O), δ, ppm: -80.7 s (CF ₃ ), -125.8 d (CF ₂ ), ² J _F , _P = 76 Hz. ³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.2 quin, ² J _P , _F = 76 Hz.

X-ray fluorescence analysis

Theoretically: Ho (25 at.%), P (75 at.%).

Experimental: Ho (29.2 at.%), P (70.8 at.%).

Elemental analysis C12F30H0O6P3:

Theoretical%: C 13.50.

Experimental%: C 13.43.

Example 13. Preparation and Characterization of Erbium (III) tris [bis (pentafluoroethyl) phosphinate], Er [(C ₂ F ₅ ) ₂ P (O) O] ₃

Er ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH - 2 He [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0 In a 50 ml round bottom flask 0.2 g (0:52 mmol) erbium (III) oxide, He ₂ 0 _3, suspended in 10 ml of water. To the suspension are added 0.96 g (3.18 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH,

added dropwise. The reaction mixture is heated to 70 ° C. with stirring. Undissolved constituents are filtered off and the

Reaction solution is concentrated at 50 ° C to dryness and the resulting solid dried for 24 hours at 100 ° C and 80 hPa. 1.08 g (1.01 mmol) of erbium (III) tris [bis (pentafluoroethyl) phosphinate],

He [(C ₂ F ₅ ) 2PO 2] 3 can be isolated as a white, finely powdered solid. Yield: 95.2%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.5 s (CF ₃ ), -125.6 d (CF ₂ ), ² J _FP = 76 Hz.

³¹ P-NMR (solvent: D ₂ O), δ, ppm: 3.4 quin, ² J _{P, F} = 76 Hz. X-ray fluorescence analysis

 Theoretically: He (25 at%), P (75 at%).

Experimental: Er (21.7 at%), P (78.3 at%). Elemental Analysis C ₁₂ ErF ₃₀ O 6 P 3:

Theoretical%: C 13.47.

Experimental%: C 13.23.

Example 14. Preparation of

Thulium (III) tris [bis (pentafluoroethyl) phosphinate], Tm [(C ₂ F ₅ ) ₂ P (O) O] ₃

Tm ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH - 2 Tm [(C ₂ F5) ₂ P (0) 0] 3 + 3 H ₂ 0

In a 50 ml round bottom flask, 0.20 g (0.52 mmol) of thulium (III) oxide,

Tm ₂ 0 ₃ , suspended in 10 ml of water. To the suspension are added 0.98 g (3.24 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH,

added dropwise. The reaction mixture is heated with stirring to 80 ° C for 3 hours. Undissolved constituents are filtered off and the reaction solution is concentrated to dryness at 50 ° C. and the remaining solid is dried for 24 hours at 100 ° C. and 80 hPa. 0.98 g (0.91 mmol) of thulium (III) tris [bis (pentafluoroethyl) phosphinate], Tm [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ , can be isolated as a white, finely powdered solid. Yield: 84.5%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.4 s (CF ₃ ), -125.5 d (CF ₂ ), JF, p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0) δ, ppm): 3.5 quin, ² J _{P, F} = 76 Hz. X-ray fluorescence analysis

 Theoretical: Tm (25 at.%), P (75 at.%).

Experimental: Tm (28.5 at.%), P (71.5 at.%).

Elemental Analysis Ci ₂ F ₃ o0 ₆ P ₃ Tm:

Theoretical%: C 13.45.

Experimental%: C 13.34. Example 15. Preparation of ytterbium (III) tris [bis (pentafluoroethyl) phosphinate], Yb [(C ₂ F ₅ ) 2P (0) 0] 3

Yb ₂ 0 ₃ + 6 (C ₂ F _{5) 2} P (0) OH "- 2 Yb [(C ₂ F ₅₎ 2 P (0) 0] 3 + 3 H ₂ 0

0.45 g (1.14 mmol) of ytterbium (III) oxide, Yb _{2 O 3 l,} are suspended in 15 ml of water in a 50 ml round bottom flask. To the suspension are added 2.04 g (6.75 mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F ₅ ) ₂ P (0) OH,

added dropwise. The reaction mixture is heated to 90 ° C with stirring for 4 hours. Undissolved constituents are filtered off and the reaction solution is concentrated to dryness at 50 ° C. and 5 hPa. 2.24 g (2.08 mmol) ytterbium (III) tris [bis (pentafluoroethyl) phosphinate],

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] 3 can be isolated as a white, finely powdered solid. Yield: 92.4%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.5 s (CF ₃ ), -125.6 d (CF ₂ ), ² J _{F, P} = 76 Hz.

³ PN R (solvent: D ₂ O), δ, ppm: 3.5 quin, ² J _Pf = 76 Hz.

X-ray fluorescence analysis

 Theoretical: Yb (25 at.%), P (75 at.%).

 Experimental: Yb (24.3 at.%), P (75.7 at.%).

Elemental Analysis Ci ₂ F ₃₀ O ₆ P ₃ Yb:

Theoretical%: C 13.39.

Experimental%: C 13.81.

Example 16. Preparation of Lutetium (III) tris [bis (pentafluoroethyl) phosphinate], Lu [(C ₂ F ₅ ) ₂ P (O) O] ₃

Lu ₂ O ₃ + 6 (C ₂ F ₅ ) ₂ P (0) OH- 2 Lu [(C ₂ F ₅ ) ₂ P (0) 0] 3 + 3 H ₂ O

In a 50 ml two-neck round bottom flask equipped with reflux condenser, 0.783 g (1.97 mmol, 15% excess) of lutetium (III) oxide, Lu ₂ O ₃ , are suspended with 9.90 g of water. To the suspension are added 2.974 g (9.85 g) mmol) of bis (pentafluoroethyl) phosphinic acid, (C ₂ F 5) ₂ P (0) OH, added dropwise. The reaction mixture is heated to 90 ° C with stirring for 6 hours. Undissolved lutetium (III) oxide is filtered off and the

Reaction solution is concentrated at 50 ° C and 0.1 hPa to dryness. 3.32 g (3.08 mmol) of lutetium (III) tris [bis (pentafluoroethyl) phosphinate],

Lu [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ can be isolated as a white, finely powdered solid. Yield: 94.0%.

¹⁹ F-NMR (solvent: D ₂ 0), δ, ppm: -80.6 s (CF ₃ ), -125.7 d (CF ₂ ), ² J _F, p = 76 Hz.

³¹ P-NMR (solvent: D ₂ 0), δ, ppm: 3.4 quin, ² J _{P, F} = 76 Hz.

X-ray fluorescence analysis

Theoretically: Lu (25 atomic%), P (75 atomic%).

Experimental: Lu (27.3 at.%), P (72.7 at.%).

Elemental Analysis C ₁₂ F ₃₀ O ₆ P ₃ Lu:

Theoretical%: C 13.37.

Experimental%: C 13.09.

Example 17: Preparation of yttrium (III) tris [bis (pentafluoroethyl) phosphinate], Y [(C ₄ F ₉ ) ₂ P (O) O] ₃

YCI ₃ + 3 Na [(C ₄ F ₉ ) ₂ P0 ₂ ] - Y [(C ₄ F ₉ ) ₂ P (0) 0] 3

In a 50 ml round-bottomed flask, 0.539 g (1.029 mmol) of sodium bis (nonafluorobutyl) phosphinate, Na [(C ₄ F ₉ ) ₂ PO ₂ ], are dissolved in 15 ml of acetone. 0.067 g (0.343 mmol) of YCl ₃ are dissolved in 6 ml of acetone and added dropwise to the phosphinate solution. Upon addition, a white precipitate of NaCl precipitates directly. The resulting suspension becomes 15

Heated to reflux for minutes. The acetone solution is decanted off and the solid washed twice with 15 ml of acetone. The combined acetone Solutions are completely concentrated. After drying, 0.757 g of crude product are obtained. The solid is extracted with 5 ml of CaCl ₂ - dried and distilled acetone and concentrated to dryness at 0.1 Pa and 50 ° C (oil bath temperature). 0.493 g (0.310 mmol) of yttrium (III) tris [bis (nonafluorobutyl) phosphinate], Y [(C ₄ F 9) ₂ PO ₂ ] 3, can be isolated as a white, finely powdered solid. Yield: 90.3%. 9F-NMR (solvent: D ₂ 0), δ, ppm: -125.85 (m, CF ₃ ), -122.08 (d, ² J _P , _F = 77 Hz, CF ₂ ), -121.19 (s, CF ₂ ) , -80.92 (m, CF ₂ ).

3 P-NMR (solvent: D ₂ 0; δ in ppm): 4.5 (quin, ² J _{P, F} = 77 Hz).

X-ray fluorescence analysis

Theoretical: Y (25 atomic%), P (75 atomic%).

Experimental: Y (43.7 atom%), P (56.3 atom%).

In addition to the deviation by the sample preparation, as explained in Example 9, the very high deviation is due to a superposition of the K line of the phosphor with the L line of the yttrium.

Elemental Analysis C ₂₄ F ₅₄ 0 ₆ P ₃ Y:

Theoretical%: C 18.11.

 Experimental%: C 18.09.

Examples of Lewis acid catalyzed reactions:

Example A: Condensation reaction of indole with benzaldehyde

Für die Katalyse mit 10 mol% werden 0.10 mmol einer Verbindung der Formel I oder einer Vergleichsverbindung, wie in Tabelle A angegeben, in einem Reaktionsgefäß vorgelegt. Benzaldehyd (1 mmol) und Indol (2 mmol) werden in 2 ml Ethanol gelöst und ins Reaktionsgefäß gegeben. Die erhaltene Lösung wird bei Raumtemperatur gerührt. Die Zeit wird jeweils in Tabelle A angegeben. Es wird der Umsatz zu 3,3'-Phenylmethylen- bis(indol) ¹H-NMR-spektroskopisch bestimmt. Die Ergebnisse sind in Tabelle A zusammengefasst.

For the catalysis with 10 mol%, 0.10 mmol of a compound of the formula I or a comparative compound, as indicated in Table A, in a reaction vessel. Benzaldehyde (1 mmol) and indole (2 mmol) are dissolved in 2 ml of ethanol and added to the reaction vessel. The resulting solution is stirred at room temperature. The time is given in Table A, respectively. The conversion to 3,3'-phenylmethylene bis (indole) ¹ H NMR spectroscopy is determined. The results are summarized in Table A.

 To isolate the final product, the solvent ethanol is removed, the residue is combined with water and the product is extracted with dichloromethane. After removal of the solvent dichloromethane and drying to obtain the isolated product 3,3'-phenylmethylene-bis (indole).

For catalysis with 1 mol%, 0.01 mmol corresponding to

Rare earth metal compound of the formula I or the comparative compound used as indicated in Table A.

Table A: Reaction conditions and results of

Condensation reaction of indole with benzaldehyde

Catalyst amount of catalyst time, hours conversion, mol%

^* Pr (CF ₃ SO ₃ ) ₃ 10 mol% 5 95 ^a

Pr [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 10 mol% 5 95 ³

* Pr (CF ₃ SO ₃ ) ₃ 1 mol% 5 89 ^a

Pr [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 5 87 ^a

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 10 mol% 6 93 ^a

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 6 82 ^a

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 5 79 ^a

Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 24 96 ^b

Gd [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 24 81 ^a

Gd [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 72 98 ^{b xx}

Gd [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 mol% 4 80 ^c

a conversions determined by H-NMR spectroscopy;

b isolated yield; ^c solvent: acetonitrile / water (v / v, 10/1)

 * not according to the invention

 ** double solvent volume

Example B: Methanolysis of octyl acetate to octanol

In an NMR tube 0.0029 mmol (10 mol%) of a compound of formula I, or a comparative compound in 0.5 ml of _CD3OD be solved.

0.290 mmol of octyl acetate are added and the reaction mixture is stirred at room temperature. The conversion determined by ¹ H-NMR spectroscopy is shown in Table B for the particular compound used

described.

The amount of catalyst is reduced as indicated in Table B.

Table B: Reaction conditions and methanolysis results of

Octyl acetate to octanol

 Catalyst amount of catalyst time, hours conversion, mol%

 Reaction at room temperature

^* Yb (CF ₃ SO ₃ ) ₃ 10 mol% 20 49 ^a

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 10 mol% 20 98 ^a

* Yb (CF ₃ SO ₃ ) ₃ 1 mol% 20 24 ³

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, 3 mol% 20 33 ^a

Reaction at 50 ° C

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, mol% 20 98 ^a

Sc [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, 3 mol% 20 99 ^a

Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, 4 mol% 24 93 ^a

Without 20 <1 ^{a a} conversions determined by ¹ H-NMR spectroscopy;

 * not according to the invention

Methanolysis of octyl acetate with ytterbium (III) bis (pentafluoroethyl) phosphinate (1 mol%)

In a 50 ml two-necked flask equipped with reflux condenser and drying tube, 0.255 mg (0.237 mmol) of ytterbium (III) tris [bis (pentafluoroethyl) phosphinate, Yb [(C ₂ F ₅ ) 2PO 2] 3, in 25 ml of CH ₃ OH solved. 4.038 g (23.70 mmol) of octyl acetate, C10H20O2, are added and the reaction mixture is stirred for 20 hours at 50 ° C. (oil bath). This gives an NMR-detected conversion of 97.8% after 20 hours

 Reaction time. Under normal pressure, the majority of the methanol is separated off. The remaining reaction mixture is washed three times with 10 ml of water. There are 2,906 g (22.31 mmol, 94% of

 theoretical yield) octanol as a clear colorless liquid.

In a corresponding reaction vessel with reflux condenser and

Drying tube are 0.025 mmol (0.5 mol%) of the compound of formula I. or the comparative compound with stirring in 16.18 mmol of 1-ethyl-3-methyl-imidazolium tris (pentafluoroethyl) trifluorophosphate, [EMIM] [FAP] suspended. 5.18 mmol of benzaldehyde and 5.63 mmol of 1-trimethyl-siloxycyclohexene are added to the catalyst suspension and stirred for 22 hours at the temperature indicated in Table C, respectively. The conversion is determined by ¹ H-NMR spectroscopy and indicated in Table C, respectively.

 For isolation, the reaction mixture with rj-hexane and

Dichloromethane / n-hexane (1: 1, v: v) extracted. The organic phases are combined and the solvents are removed in vacuo. Optionally, hydrolysis with tetrahydrofuran-water (4: 1, v: v) and renewed extraction with n-hexane follows. After removal of the solvent in vacuo, the isomer mixture is obtained. In the case of a 2nd cycle, the remaining [EMIM] [FAP] phase becomes

(after product extraction) from the first pass at 0.1 hPa and room temperature. Then 4.00 mmol of benzaldehyde and 4.31 mmol of 1-trimethyl-siloxycyclohexene are added. After the time indicated in Table C, work up and isolate as previously described.

Table C: Reaction conditions and results of the Mukaiyama-aldol reaction of benzaldehyde with 1- (trimethylsiloxy) cyclohexene with 0.5 mol% catalyst in the solvent [EMIM] [FAP]

 Catalyst Time, Std. Sales, mol% Yield,%

 Reaction at 25 ° C

La [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 22 91 ^a -

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 22 96 ^a 90

2nd cycle 23 98.5 ^a 80

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 4 99 ^a - without 192 82 ^a

Reaction at 50 ° C Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.75 88 ^a -

Time extended to 2 97 ^a 95

Sc [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, 75 99 ^a 87.5

La [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1, 75 99 ^a 89 ³

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 2 87 ^a 86

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 98 ^a 90

* Yb (CF ₃ S0 ₃ ) ₃ 0.5 89 ^a -

* Pr (CF ₃ S0 ₃ ) ₃ 3.5 85 ^a - without 6 90 ^a

a conversions determined by ¹ H-NMR spectroscopy;

 * not according to the invention

Example D: Friedel-Crafts alkylation of anisole with

 As solvents for Friedel-Crafts alkylation with compounds of the formula I, 1,2-dichloroethane (DCE), [EMIM] [FAP] (IL) or aprotic solvents can be used. This reaction is also possible without solvents, since the compounds of formula I are soluble in cyclohexyl methanesulfonate as well as in the by-produced methanesulfonic acid. By adding anisole in excess, the proportion of the

Multiple alkylation be reduced, whereas an addition of the

Alkylating agent cyclohexylmethanesulfonate in the ratio 3: 1 to anisole quantitatively gives the triply alkylated compound.

The ortho / para ratio of the methoxy group in the final product depends on the chosen catalyst and solvent.

Method: To 6 mmol of cyclohexylmethanesulfonate and 8.75 mmol of anisole 0.56 mmol of the compound of formula I or der Reference compound and the corresponding solvent according to Table D added. The suspension obtained is heated according to the time in Table D at 80 ° C. If possible, the solvent is removed in vacuo. The residue obtained is a two-phase system. The upper phase consists almost exclusively of methanesulfonic acid with traces of the products and the lower phase of product. Both phases are extracted with H ₂ O and diethyl ether. Alternatively, the reaction mixture can be mixed with dichloromethane and shaken out with H ₂ 0.

Table D contains a summary of the results of the Friedel-Crafts alkylation of anisole with cyclohexyl methanesulfonate at 80 ° C., catalysis with 10 mol%

 Catalyst solvent time, min conversion, mol%, ratio o / p

* Yb (CF ₃ S0 ₃ ) ₃ DCE 180 99 ^a o / p = 1/2

La [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ DCE 180 99 ^a , o / p = 3/1

Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ IL 60 99 ^a , o / p = 2/1

Gd [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ without 180 99 ^a , o / p = 1/1

a conversions determined by H-NMR spectroscopy;

* not according to the invention

A direct comparison of the La-phosphinate used to yterbium triflate with the same solvent and for the same time shows a significantly different ratio of ortho to para substitution.

Example E: Friedel-Crafts alkylation of Durol with

Cyclohexylmethansulfonat

According to H. Kotsuki, T. Ohishi, M. Inoue, T. Kojima, Synthesis 1999, 4, 603, neither scandium triflate nor trifluoromethanesulfonic acid catalyzes the reaction of 1,2,4,5-tetramethylbenzene with the alkylating agent

 Cyclohexylmethanesulfonate to 1-cyclohexyl-2,3,5,6-tetramethylbenzene.

However, the catalysts of the formula I according to the invention can be used in this reaction.

Catalysis with yttrium (III) tris [bis (pentafluoroethyl) phosphinate]

 (10 mol%):

 In a 50ml two-necked flask equipped with reflux condenser and

 Drying tube are added to a suspension of 0.285 g (0.29 mmol)

Yttrium (III) tris [bis (pentafluoroethyl) phosphinate], Y [(C ₂ F 5) ₂ P0 ₂ ] 3, in 10 mL of 1, 2-dichloroethane, 0.577 g (3.24 mmol) of cyclohexylmethanesulfonate and 0.587 g (4.37 mmol) of 1 Added 2,4,5-tetramethylbenzene (Durol). The

Reaction mixture is stirred at 80 ° C for 15 hours. The conversion is determined by H-NMR spectroscopy after 15 hours and is 65 mol% (based on cyclohexyl methanesulfonate). The conversion based on 1, 2,4,5-tetramethylbenzene corresponds to 26.5%. To the reaction mixture is added 15 ml of dichloromethane and the organic phase is washed 3 times with 30 ml of H ₂ O. Subsequently, the solvents are removed in vacuo at 0.1 Pa. Excess 1, 2,4,5-tetramethylbenzene and the resulting methanesulfonic acid are at 0.1 Pa and 30 ° C. (Oil bath temperature) removed. 0.20 g of 1-cyclohexyl, 2,3,5,6-tetramethylbenzene, C ₁₆ H ₂ , can be obtained from the residue by sublimation at 0.1 Pa and 70 ° C (oil bath temperature). Catalysis with scandium (III) tris [bis (pentafluoroethyl) phosphinate] (10 mol%): In a 50ml two-necked flask equipped with reflux condenser and

Drying tube are added to a suspension of 0.267 g (0.28 mmol)

Scandium (III) tris [bis (pentafluoroethyl) phosphinate], Sc [(C ₂ F ₅ ) ₂ PO ₂ ] 3, in 5 ml of 1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate,

[EMIM] [FAP], 0.526 g (2.95 mmol) of cyclohexylmethanesulfonate and 0.393 g (2.93 mmol) of 1, 2,4,5-tetramethylbenzene (Durol) were added. The

Reaction mixture is stirred for 6 hours at 80 ° C under reflux. The conversion is determined by ¹ H-NMR spectroscopy after 6 hours and is 80 mol% (based on cyclohexyl methanesulfonate). The conversion based on 1, 2,4,5-tetramethylbenzene corresponds to 34%. By sublimation at 35 ° C (oil bath) and 0.1 Pa 0.10 g (0.463 mmol) of 1-cyclohexyl-2,3,5,6-tetramethylbenzene can be isolated.

Example F: Friedel-Crafts acylation of anisole to 4-methoxyacetophenone using acetic anhydride as the acylating agent

2.503 mmol of the compound of the formula I correspondingly given in Table F are dissolved in 58 mmol of 1-ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate [EMIM] [FAP] in a 50 ml

Two-necked flask suspended. For this purpose, 50 mmol of anisole and 00.0 mmol of acetic anhydride are added. The reaction mixture is

stirred according to the conditions of Table F. Preference is given to working under reduced pressure, as this allows the resulting acetic acid to be removed from the system. By ¹ H NMR spectroscopy calculated conversion to 4-methoxyacetophenone is listed in Table F. 4-methoxy-acetophenone is detected in the reaction mixture by ¹ H-NMR spectroscopy. The product can also be isolated by extraction with hexane, chloroform and hexane.

The amount of catalyst is varied according to the data in Table F.

Table F: Reaction conditions and results of Friedel-Crafts acylation of anisole with acetic anhydride in solvent [EMIM] [FAP]

a conversions determined by ¹ H-NMR spectroscopy;

 * not according to the invention

Example G: Mannich reaction of benzaldehyde with aniline and

 Trimethylsiloxycyclohexen

Bei der literaturbeschriebenen Reaktion mit 20 mol% Yb(CF₃S0₃)3 [T. Akiyama, J. Takaya, H. Kagoshima, Adv. Synth. Catal. 2002, 344, 338.] kann eine Ausbeute von 83 % nach einer Reaktionszeit von 12 h ermittelt werden. [(CH ₃ ) ₃ SiOH]

In the literature described reaction with 20 mol% Yb (CF ₃ S0 ₃ ) 3 [T. Akiyama, J. Takaya, H. Kagoshima, Adv. Synth. Catal. 2002, 344, 338.], a yield of 83% can be determined after a reaction time of 12 h.

With the catalysts of formula I according to the invention succeeds

Reaction with a smaller amount of catalyst. It arises

Isomers.

rule:

In a suitable reaction vessel with reflux condenser and drying tube are 0.01 mmol of the compound of formula I, as in Table G

in 1.9 mmol of 1-ethyl-3-methyl-imidazolium tris (pentafluoroethyl) trifluorophosphate, [EMIM] [FAP]. 9.88 mmol of benzaldehyde and 10.29 mmol of aniline are added to the suspension. The third component is 5 mmol

 Trimethylsiloxycyclohexen added and the reaction mixture is stirred in the time indicated in Table G at room temperature. The extraction of the product is carried out with π-hexane and ethyl acetate. The

Solvent is removed at RT and 0.1 Pa. By washing the

Residue with diethyl ether can isolate the product 2- [1'-phenyl-1 '- (/ V-phenyl) amino) methyl] cyclohexanone in 90% purity.

Table G: Reaction conditions and results of the Mannich reaction of benzaldehyde with aniline and trimethylsiloxycyclohexene in [EMIM] [FAP] (IL)

Catalyst amount, solvent time, h conversion, isomermol% mol%, ratio

 (Yield syn / anti

%)

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 IL 20 93 ^a (24) 55/45 Sc [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 1 IL 72 93 ^a 66/34

Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 2 IL 2 95 ^a 74/26

 (50 ° C)

 65

La [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 2 IL 16.5 95 ^a (68) 63/37 ^a Revenues determined by H NMR spectroscopy;

Example H: Diels-Alder reaction of 2,3-dimethylbutadiene with

methyl vinyl ketone

The literature known reaction [C. E. Song, E.J. Roh, S.-g. Lee, W.H. Shim, J.H. Choi, Chem. Commun. 2001, 122] to 1- (3,4-dimethylcyclohex-3-enyl) ethanone in the presence of scandium triflate proceeds at room temperature with an isolated yield of 88% after 4 hours reaction time. The amount of catalyst of scandium triflate is 0.2 mol%. The realization of this reaction with compounds of the formula I as catalyst is carried out at room temperature in [EMIM] [FAP], in 1, 2-dichloroethane or without solvent.

rule:

 In a suitable reaction vessel with reflux condenser and drying tube are 0.00671 mmol of the compound of formula I or the

Comparative compound, as indicated in Table H, suspended in 3.31 mmol of 1-ethyl-3-methyl-imidazolium-tris (pentafluoroethyl) trifluorophosphate [EMIM] [FAP] or suspended in 1, 2-dichloroethane or initially charged. 3.8 mmol of methyl vinyl ketone and 7.3 mmol of 2,3-dimethylbutadiene are added to this suspension or the pure substance and the Reaction mixture in the time indicated in Table H and the

stirred temperature. The conversion to 1- (3,4-dimethylcyclohex-3-enyl) ethanone is determined by H-NMR spectroscopy. The isolation of the product can be carried out by extraction with chloroform.

Table H: Reaction conditions and results of the Diels-Alder reaction of 2,3-dimethylbutadiene with methyl vinyl ketone (catalyst 0.2 mol%)

 Temperature, turnover in mol%

Catalyst solvent time, h

 ° C (yield),%

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] 3 [EMI lfFAP] 25 19 75 ^a

without 25 48 56 ^a

CH ₂ CICH ₂ CI 25 48 26 ^a

[EMIM] [FAP] 50 2 89 ^a (83)

[EMIM] [FAP] 70 4 99 ^a (68)

"CH ₂ CICH ₂ CI 70 10 93 ^a (83)

YbF (C ₂ F ₅ ) ₂ P0 ₂ ] ₃ [EMIM] [FAP] 50 4 84 ^a

Yb [CF ₃ S0 ₃ ] ₃ [EMIM] [FAP] 50 4 80 ^{a a} Sales determined by ¹ H NMR spectroscopy;

Example I: Diels-Alder reaction of 2,3-dimethylbutadiene with

maleic anhydride

For the reaction with maleic anhydride, the

Tris [bis (pentafluoroethyl) phosphinates] of scandium, lanthanum, cerium and ytterbium with a catalyst amount of 0.1 mol% in [EMIM] [FAP]. The ionic liquid with the catalyst can be used after drying for a second catalytic pass without loss of catalytic activity.

rule:

 In a suitable reaction vessel with a drying tube, 0.002 mmol of the compound of the formula I, as indicated in Table I, in 3.9 mmol of 1-ethyl-3-methyl-imidazolium tris (pentafluoroethyl) trifluorophosphate,

[EMIM] [FAP], suspended. 1.63 mmol of maleic anhydride and 7.33 mmol of 2,3-dimethylbutadiene are added sequentially. The reaction takes place with stirring at the indicated temperatures. The conversion to 3a, 4,7,7a-tetrahydro-5,6-dimethylisobenzofuran-1, 3-dione is determined by the indicated reaction time by means of ¹ H-NMR spectroscopy. Isolation is carried out by extraction with chloroform. The crude product can be washed with acetonitrile.

Passage 2:

 The catalyst phase is dried at 0.1 Pa and 50 ° C oil bath temperature and used again. The quantities correspond to the specifications of the general regulation.

Table I: Reaction conditions and results of the Diels-Alder reaction of 2,3-dimethylbutadiene with maleic anhydride (catalyst 0.1 mol%)

 Temperature, turnover in mol%

Catalyst solvent time, h

 ° C (yield),%

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ [EMIM] [FAP] 25 2 99 ^a (80)

2nd passage 2 99 ^a (80)

Sc [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ [EMIM] [FAP] 0 4 97 ^a (71)

La [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ [EMIM] [FAP] 0 4 85 ^a

Yb [(C ₂ F _{5) 2} P0 _{2] 3} [EMIM] [FAP] 0 4 (95) Example J: Aza-Diels-Alder reaction of (E) -A / -Benzylidenaniline with

 tadien)

When using [EMIM] [CF ₃ SO ₃ ] as the solvent and "microencapsulated" scandium (III) trifluoromethanesulfonate as catalyst, the reaction of benzylideneaniline and Danishefsky's diene reported in the literature gives 67% yield over a reaction time of 20 hours [F. Zulfiqar, T. Kitazume, Green Chemistry 2000, 2, 137]

Catalyst amount of "microencapsulated" scandium (III) trifluoromethanesulfonate (10-15% Sc (CF ₃ SO ₃ ) 3) to 50 mg total catalyst is 0.5 mol%.

In a suitable reaction vessel with a drying tube, the corresponding amount of catalyst of the compound of formula I or the comparative compound, as indicated in Table J, in 4.34 mmol

[EMIM] [CF ₃ S0 ₃ ] suspended. To the suspension are added 3.15 mmol of (E) - / V-benzylideneaniline and 3.12 mmol of (E) - (4-methoxybuta-1,3-dien-2-yloxy) trimethylsilane (Danishefsky diene) and the

Reaction mixture stirred at room temperature. After the time indicated in Table J, the conversion is determined by ¹ H NMR spectroscopy. For isolation, the crude product is extracted with diethyl ether and the

Diethyl ether is removed in vacuo at 50 hPa. The addition of

Hydrochloric acid in the isolation may be preferred. Table J: Reaction conditions and results of the aza-Diels-Alder reaction of (E) - / V-benzylideneaniline with Danishefsky diene

room temperature

 Amount, solvent time turnover, mol%

catalyst

 mol% (yield,%)

Sc [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [CF ₃ S0 ₃ ] 10 min 93 ^a (96)

2nd passage 60 min 95 ^a (90)

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [CF ₃ S0 ₃ ] 10 min 99 ^a (78)

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [CF ₃ S0 ₃ ] 10 min 98 ^a (61)

^* Yb [0 ₃ SCF ₃ ] ₃ 0.5 [EMIM] [CF ₃ S0 ₃ ] 10 min 98 ^a (30)

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [FAP] 30 min 86 ^a

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.01 [E IM] [FAP] 20 h 99 ^a (78)

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.01 [EMIM] [FAP] 24 h 99 ^{a a} Sales determined by H-NMR spectroscopy;

b isolated product, purity 90%

* not according to the invention

Example K: Michael reaction of methoxy-methyl (trimethylsiloxy) propene with methyl vinyl ketone

In einem geeigneten Reaktionsgefäß werden 0.03 mmol der in Tabelle K angegebenen Verbindung der Formel I oder die Vergleichsverbindung in 1.917 mmol [EMIM][FAP] suspendiert. Zu der Suspension werden 5.28 mmol Methylvinylketon und 4.83 mmol (1-Methoxy-2-methylprop-1 - enyloxy)trimethylsilan hinzugefügt. Das Reaktionsgemisch wird bei Raumtemperatur gerührt. Nach der in Tabelle K angegebenen

0.03 mmol of the compound of the formula I given in Table K or the comparative compound are suspended in 1,917 mmol of [EMIM] [FAP] in a suitable reaction vessel. 5.28 mmol of methyl vinyl ketone and 4.83 mmol of (1-methoxy-2-methylprop-1-enyloxy) trimethylsilane are added to the suspension. The reaction mixture is stirred at room temperature. After the given in Table K.

Reaction time, the conversion is determined by ¹ H NMR spectroscopy. Isolation is by extraction with chloroform and removal of the

Solvent at RT and 0.1 Pa possible. An isomer mixture is formed.

When water is added during extraction with chloroform, hydrolysis is carried out to give methyl 2,2-dimethyl-5-oxohexenoate. This is indicated in Table K. The remaining after the work-up (product extraction)

 [EMIM] [FAP] phase is dried at 0.1 hPa and room temperature and can be used for a second pass.

Table K: Reaction conditions and results of the Michael reaction of methoxy-methyl (trimethylsiloxy) propene with methyl vinyl ketone at room temperature

Catalyst amount solvent time conversion (mol%) E / Z ^a

 (mol%) (Yield,%)

Y [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [FAPl 10 min 99 ^a (72) 62/38

2nd round 0.5 [EMIM] [FAP] 10 min 99 ^a (64) 61/39

Yb [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIM] [FAP] 10 min 99 ^a (83 ^b ) 61/39

^* Yb [0 ₃ SCF ₃ ] ₃ 0.5 [EMIM] [FAP] 10 min -

Ce [(C ₂ F ₅ ) ₂ P0 ₂ ] ₃ 0.5 [EMIMHFAP] 20 h 96 ^a (35) 66/34 ^a determined by ¹ H NMR spectroscopy; ^b methoxy-dimethyl-oxohexenoate;

* not according to the invention

For comparison, the catalytic reaction with Yb (CF ₃ SO ₃ ) _{3 is performed} in [EMIM] [FAP]. With a catalyst amount of 0.5 mol%, a complete consumption of the methyl vinyl ketone can be determined after 10 min. in the Difference to the reaction with ytterbium (lil) - bis (pentafluoroethyl) phosphinate occurs with the addition of

Methoxymethyl (trimethylsiloxy) propene to the reaction mixture in addition to gas evolution a significant yellowing of the solution. After evaluation of the ¹ H-NMR spectra of the reaction mixtures and CHCI ₃ - extracts is to assume that under the given conditions, a polymerization of the starting materials.

Example L: Mukaiyama aldol reaction as described in Example C with

In a 50 ml two-necked flask with reflux condenser and drying tube, 0.033 g (0.021 mmol) of yttrium (III) tris [bis (nonafluorobutyl) phosphinate] Y [(C ₄ F ₉ ) ₂ PO ₂ ] 3 with stirring in 4.875 g (8.76 mmol) 1-Ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate [EMIM] [FAP]

suspended. To the suspension are added 0.51 1 g (4.82 mmol) of benzaldehyde and 0.965 g (5.67 mmol) of 1-trimethylsiloxycyclohexene. The reaction mixture is stirred for 4 hours at 50 ° C oil bath temperature. The determined by ¹ H spectroscopy sales after 120 minutes, 65 mol% and after 240 minutes 82 mol%. The batch is extracted twice with 20 ml of chloroform. The solvent phases are combined and the solvent removed in vacuo. This gives 1 .084 g of 2-phenyl (trimethylsiloxy) methylcyclohexane, C16H24O2S1, as crude product. The hydrolysis is carried out with a tetrahydrofuran-water mixture (10: 1, v: v). Extraction with twice 20 ml of n-hexane and concentration to dryness in vacuo gives 0.766 g (3.75 mmol, 78% of theoretical

Yield) of the isomer mixture of 2-

(Hydroxyphenylmethyl) cyclohexanone, Ci ₃ H ₁₆ O ₂ as a white solid. The molar isomer ratio of syn-2- (hydroxyphenylmethyl) cyclohexanone to a / 7f / ^' -2- (hydroxyphenylmethyl) cyclohexanone is 1: 1 .6 ( ¹ H-NMR).

Claims

 claims Use of at least one compound of formula I [RE] ²⁺ z [(R _f ) ₂ P (0) 0] - I,  where RE is a rare earth metal,  z corresponds to the charge of the rare earth metal cation and R _{f are} each independently trifluoromethyl, pentafluoroethyl, so-heptafluoropropyl, n-heptafluoropropyl, n-nonafluorobutyl, iso-Nonafluorbutyl, sec-nonafluorobutyl or Fe Y. Nonafluorbutyl means, as a Lewis acid catalyst. Use according to claim 1, wherein RE in formula I is selected from the rare earth metals Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb. 3. Use according to claim 1 or 2, wherein z is 2, 3 or 4. 4. Use according to claim 3, wherein z is 3. 5. Use according to one or more of claims 1 to 4, wherein RE in formula I is selected from Sc, Y, Yb and Lu. 6. Use according to one or more of claims 1 to 5, wherein R _f represents in formula I, pentafluoroethyl, or n-nonafluorobutyl. 7. Compounds of the formula II [RE] ^{Z +} z [(C ₂ F ₅ ) ₂ P (O) O] - II,  wherein RE represents a rare earth metal selected from Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and  z corresponds to the charge of the rare earth metal cation. 8. Compounds of the formula III [RE] ^{Z +} z [(nC ₄ F ₉ ) ₂ P (O) O] - III, wherein RE represents a rare earth metal selected from Sc, Y, Lu, La, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho and Tm and z corresponds to the charge of the rare earth metal cation. Process for the preparation of compounds according to Claim 7 or 8, characterized in that bis (pentafluoroethyl) phosphinic acid or bis (n-nonafluorobutyl) phosphinic acid is reacted with an oxide or carbonate of the rare earth metal RE or with the rare earth metal RE as such, the rare earth metal being RE is selected according to claim 7 or 8. A Lewis acid catalyst according to one or more of claims 1 to 8 for use in a Lewis acid catalyzed reaction selected from a condensation reaction, alcoholysis, aldol reaction, Mukaiyama-aldol reaction, Gattermann-Koch reaction, Beckmann and Fries rearrangement, Friedel-Crafts acylation, Friedel-Crafts alkylation, Mannich reaction, Diels-Alder reaction, aza-Diels-Alder reaction, Baylis-Hillman reaction, Reformatsky reaction, Claisen rearrangement, Prins cyclization reaction, Allylation of  Carbonyl compounds, cyanation of aldehydes and ketones, 1, 3-dipolar cycloaddition or Michael reaction.