# Patent

## Title
Compounds with (perfluoroalkyl) fluorohydrogenphosphate anions

## Abstract

The present invention relates to a process for the preparation of compounds with (perfluoroalkyl)fluorohydrogenphosphate anion, and to compounds containing (perfluoroalkyl)fluorohydrogenphosphate anion and to the use thereof.

## Background
The present invention relates to a process for the preparation of compounds with (perfluoroalkyl)fluorohydrogenphosphate anion, and to compounds with (perfluoroalkyl)fluorohydrogenphosphate anion and to the use thereof.
Onium salts with perfluoroalkylfluorophosphate anions (FAP anions) are employed as ionic liquids and conductive salts [EP 0929558 B1, WO 02/085919 A1, EP 1162204 A1].
An ionic liquid is taken to mean salts which generally consist of an organic cation and an inorganic anion. They do not contain any neutral molecules and usually have melting points below 373 K [Wasserscheid P, Keim W, 2000, Angew. Chem. 112: 3926].
Onium salts with an organic cation and a perfluoroalkylfluorophosphate anion (FAP anion) are usually prepared via an exchange reaction of a water-soluble onium salt with, for example, a chloride, bromide, tetra-fluoroborate or triflate anion and perfluoroalkylfluorophosphoric acid (HFAP) or its alkali-metal salts in water [N. V. Ignatyev, U. Welz-Biermann, A. Kucheryna, G. Bissky, H. Willner, 2005, J. Fluorine Chem. 126: 1150-1159]. HFAP [WO 03/002579] and metal salts thereof can be prepared from tris(perfluoroalkyl)difluorophosphoranes, which can be obtained by electrochemical fluorination (Simons process) of trialkylphosphines [N. V. Ignatyev, P. Sartori, 2000, J. Fluorine Chem. 103: 57-61; WO 00/21969]. Organic salts with an FAP anion usually have limited water solubility and can easily be separated from by-products, which remain in the aqueous solution.
Ionic liquids with FAP anion have high electrochemical and thermal stability and low viscosity. Areas of application of these ionic liquids are found in organic chemistry (solvents, extraction media, etc.) and in the material sciences (heat-exchange media, lubricants, conductive salts, etc.). Ionic liquids having FAP anions are inert materials which have much better hydrolytic stability than, for example, ionic liquids having PF6− anions. In some cases, however, a medium is desirable which can easily be broken down again after the respective process.
The aim of the present invention was thus firstly the provision of a novel process for the preparation of compounds containing (perfluoroalkyl)fluorohydrogenphosphate anions. A further aim of the present invention was the provision of novel compounds containing (perfluoroalkyl)fluorohydrogenphosphate anions.
WO 03/087113 discloses a process which facilitates the reduction of (perfluoroalkyl)fluorophosphoranes. Surprisingly, a process has now been found which facilitates the addition of a hydride ion onto the substrate during the reaction of (perfluoroalkyl)fluorophosphorane with a hydride ion donor, giving a (perfluoroalkyl)fluorohydrogenphosphate anion.
The present invention thus relates firstly to a process for the preparation of a compound of the formula (1)

[Kt]x+[(CnF2n+1)zPF5-zH]−x  (1)

in which [Kt]x+ is an inorganic or organic cation,
where, in one step, a compound of the formula (2)

(CnF2n+1)zPF5-z  (2)

is reacted with a hydride ion donor,
and where, if [Kt]x+ is an organic cation, a second step can optionally be carried out in which the product from the first step is reacted with a compound of the formula (3)

[Kt]x+[X]−X  (3),

in which [Kt]x+ stands for an organic cation and [X]− stands for a hydrophilic anion,
in which n=1-8, x=1-4 and z=1-4.
In the literature, bis(trifluoromethyl)difluorohydrogenphosphate ([(CF3)2PF3H]−) and trifluoromethyltrifluorohydrogenphosphate ([CF3PF4H]−) salts with K+ cation and [Me2NH2]+ cation are described [J. F. Nixon, J. R. Swain, 1968, Chem. Comm.: 997-998; J. F. Nixon, J. R. Swain, 1970, J. Chem. Soc. A: Inorg. Phys. Theor.: 2075-2080; R. G. Cavell, J. F. Nixon, 1964, Proc. Chem. Soc.: 229]. K+ [(CF3)2PF3H]− and K+ [CF3PF4H]− salts are prepared in situ in a reaction of bis(trifluoromethyl)fluorophosphine ((CF3)2PF) or trifluoromethyldifluorophosphine (CF3PF2) with potassium bifluoride in a sealed test tube at 60 to 100° C. or in acetonitrile solution at room temperature. The corresponding salts with a [Me2NH2]+ cation are obtained by the reaction of CF3PF2 or (CF3)2PF with Me2NH.
These salts have merely been investigated with the aid of 19F- and 1H-NMR spectroscopic measurements in the reaction mixture. For the synthesis of [(CF3)2PF3H]− and [CF3PF4H]− salts by the method of J. F. Nixon and J. R. Swain, the two starting materials bis(trifluoromethyl)fluorophosphine (CF3)2PF and trifluoromethyldifluorophosphine CF3PF2, which are in the gaseous state at room temperature and are highly air-sensitive, are necessary. These can be prepared in a complex, multistep synthesis process.
In accordance with the invention, hydride ion donors are compounds which are capable of releasing one or more hydride ions (H−). In the process according to the invention, the hydride ion donor is preferably selected from the group comprising metal hydrides, borohydrides, hydridoborates and hydridoaluminates, but also tertiary and secondary amines.
In a particularly preferred embodiment, metal hydrides are employed; these are very particularly preferably LiAlH4.
In a further particularly preferred embodiment, use is made of tertiary or secondary amines of the formula (11):

R142N—CH2R15  (11),

where
R14 and R15 on each occurrence, independently of one another, denotes

    
    
        H, where a maximum of one substituent R14 can be H,
        straight-chain or branched alkyl having 1-20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where R15 may also be Cl or F,
where R15 may be fully substituted by fluorine and/or one or more R14 and/or R15 may be partially substituted by halogens or partially substituted by —OR1*, —NR1*2, —CN, —C(O)NR1*2 or —SO2NR1*2,
and where one or two non-adjacent carbon atoms which are not in the α-position of the radicals R14 and/or R15 may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R1*2—, —C(O)NR1*—, —SO2NR1*— or —P(O)R1*—;
in which R1* stands for non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl.
The hydride ion donor used after the process according to the invention can be employed either in excess or in equimolar amount, in each case based on the amount of (perfluoroalkyl)fluorophosphoranes employed. The hydride ion donor is preferably employed in equimolar amount.
(Perfluoroalkyl)fluorophosphoranes of the formula (2) can be prepared by conventional methods known to the person skilled in the art. These compounds are preferably prepared by electrochemical fluorination of suitable starting compounds [V. Y. Semenii et al., 1985, Zh. Obshch. Khim. 55 (12): 2716-2720; N. V. Ignatyev, P. Sartori, 2000, J. Fluorine Chem. 103: 57-61; WO 00/21969].
In the compound of the formula (2), z preferably stands for 2 or 3; this means that formula (2) is preferably selected from the group comprising (CnF2n+1)3PF2 and (CnF2n+1)2PF3. z is particularly preferably =3.
In the compounds of the formula (2), n likewise preferably stands for 2, 3 or 4, particularly preferably for 2 or 4. n very particularly preferably stands for 2, this means that a compound of the formula (2) is very particularly preferably (C2F5)zPF5-z.
The compounds of the formula (2) are thus very particularly preferably (C2F5)3PF2.
The cation [Kt]x+ in formula (1) of the process according to the invention can be either an inorganic cation or an organic cation.
If an inorganic cation is present, this is preferably a metal cation. The metal cation is particularly preferably an alkali-metal cation, preferably a lithium, sodium or potassium cation.
If [Kt]x+ in formula (1) is an organic cation, this is preferably selected, exactly like [Kt]x+ in formula (3), from the group comprising ammonium, phosphonium, uronium, thiouronium, sulfonium, oxonium, guanidinium cations, heterocyclic cations and iminium cations, as defined below:
Ammonium cations are given by the general formula (4)

[NR4]+  (4),

where
R in each case, independently of one another, denotes

    
    
        H,
        straight-chain or branched alkyl having 1-20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where one R may be fully substituted by fluorine and/or one or more R may be partially substituted by halogens, in particular —F and/or Cl, or partially substituted by —OR1, —NR1*2, —CN, —C(O)NR12 or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of the radical R may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1— or —P(O)R1—.
Phosphonium cations are given by the general formula (5)

[PR24]+  (5),

where
R2 in each case, independently of one another, denotes

    
    
        H where all substituents R2 cannot simultaneously be H, NR12,
        straight-chain or branched alkyl having 1-20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where one R2 may be fully substituted by fluorine and/or one or more R2 may be partially substituted by halogens, in particular —F and/or —Cl, or partially substituted by —OR1, —CN, —C(O)NR12 or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of the R2, may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, or —P(O)R1—.
Cations of the formulae (4) and (5) in which all four or three substituents R and R2 are fully substituted by halogens, for example the tris(trifluoromethyl)methylammonium cation, the tetra(trifluoromethyl)ammonium cation or the tetra(nonafluorobutyl)ammonium cation, are therefore excluded.
Uronium cations are given by the general formula (6)

[C(NR3R4)(OR5)(NR6R7)]+  (6)

and suitable thiouronium cations are given by the formula (7),

[C(NR3R4)(SR5)(NR6R7)]+  (7),

where
R3 to R7 each, independently of one another, denote

    
    
        H, NR1*2,
        straight-chain or branched alkyl having 1 to 20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where one or more of the substituents R3 to R7 may be partially substituted by halogens, in particular —F, or by —OH, —OR1, —CN, —C(O)NR12 or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of R3 to R7 may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, or —P(O)R1—.
Sulfonium cations are given by the general formula (12))

[(Ro)3S]+  (12),

where
Ro stands for

    
    
        NR′′′2,
        straight-chain or branched alkyl having 1-8 C atoms,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where one or more of the substituents R0 may be partially substituted by halogens, in particular —F, or by —OR′′′, —CN or —N(R′′′)2.
Oxonium cations are given by the general formula (13)

[(Ro+)3O]+  (13),

where
Ro* stands for

    
    
        straight-chain or branched alkyl having 1-8 C atoms,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
        
            where one or more of the substituents R0* may be partially substituted by halogens, in particular —F, or by —OR′′′, —CN or —N(R′′′)2, in which R′′′ stands, independently of one another, for a straight-chain or branched C1-C8-alkyl.
        
        
    
    


Ro and Ro* here preferably stand for a straight-chain alkyl having 1-8 C atoms, unsubstituted phenyl, or phenyl which is substituted by C1-C6-alkyl, OR′′′, N(R′′′)2, CN or F.
R′′′ preferably stands for a straight-chain alkyl having 1-8 C atoms, in particular methyl or ethyl.
Guanidinium cations are given by the general formula (8)

[C(NR8R9)(NR10R11)(NR12R13)]+  (8),

where
R8 to R13 each, independently of one another, denote

    
    
        H, NR1*2,
        straight-chain or branched alkyl having 1 to 20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where one or more of the substituents R8 to R13 may be partially substituted by halogens, in particular —F, or by —OR1, —CN, —C(O)NR12 or —SO2NR12, and where one or two non-adjacent carbon atoms which are not in the α-position of R8 to R13 may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, or —P(O)R1—.
Heterocyclic cations are given by the general formula (9)

[HetN]+  (9),

where [HetN]+ is a heterocyclic cation selected from the group comprising










where the substituents R1′ to R4′ each, independently of one another, denote

    
    
        H,
        straight-chain or branched alkyl having 1-20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
        saturated, partially or fully unsaturated heteroaryl, heteroaryl-C1-C6-alkyl or aryl-C1-C6-alkyl,
    
    


where the substituents R1′, R2′, R3′ and/or R4′ together may form a ring system,
where one or more substituents R1′ to R4′ may be partially or fully substituted by halogens, in particular —F and/or —Cl, or partially substituted by —OR1, —CN, —C(O)NR12 or —SO2NR12, but where R1′ and R4′ cannot simultaneously be fully substituted by halogens, and where one or two non-adjacent carbon atoms which are not bonded to the heteroatom of the substituents R1′ to R4′, may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, or —P(O)R1—.
Iminium cations are given by the general formula (10)

[R142N═CHR15]+  (10),

where
R14 and R15 on each occurrence, independently of one another, denotes

    
    
        H, where a maximum of one substituent R14 can be H,
        straight-chain or branched alkyl having 1-20 C atoms,
        straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
        straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
        saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
    
    


where R15 may also stand for Cl or F,
where R15 may be fully substituted by fluorine and/or one or more R14 and/or R15 may be partially substituted by halogens or partially substituted by —OR1*, —NR1*2, —CN, —C(O)NR1*2 or —SO2NR1*2,
and where one or two non-adjacent carbon atoms which are not in the α-position of the radical R14 and/or R15 may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R1*2—, —C(O)NR1*—, —SO2NR1*— or —P(O)R1*—;
R1 in all above-mentioned definitions stands for H, non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl, and R1*stands for non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl.
Fully unsaturated cycloalkyl substituents in the sense of the present invention are also taken to mean aromatic substituents.
In accordance with the invention, suitable substituents R and R2 to R13 of the compounds of the formulae (4) to (8), besides H, are preferably: C1- to C20—, in particular C1- to C14-alkyl groups, and saturated or unsaturated, i.e. also phenyl, C3- to C7-cycloalkyl groups, which may be substituted by C1- to C6-alkyl groups, in particular phenyl.
The substituents R and R2 in the compounds of the formula (4) or (5) may be identical or different. In compounds of the formulae (4), three or four substituents R are preferably identical. In compounds of the formulae (5), the substituents R2 are preferably different.
The substituents R and R2 are particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.
Up to four substituents of the guanidinium cation
[C(NR8R9)(NR10R11)(NR12R13)]+ may also be connected in pairs in such a way that mono-, bi- or polycyclic molecules form.
Without restricting generality, examples of such guanidinium cations are:




where the substituents R8 to R10 and R13 may have an above-mentioned or particularly preferred meaning.
The carbocycles or heterocycles of the above-mentioned guanidinium cations may optionally also be substituted by C1- to C6-alkyl, C1- to C6-alkenyl, CN, NR12, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3 or SO2NR12, where R1 has an above-mentioned meaning, substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle.
Up to four substituents of the thiouronium cation [C(NR3R4)(SR5)(NR6R7)]+ may also be connected in pairs in such a way that mono-, bi- or polycyclic molecules form.
Without restricting generality, examples of such thiouronium cations are indicated below:




in which Y═S
and where the substituents R3, R5 and R6 may have an above-mentioned or particularly preferred meaning.
The carbocycles or heterocycles of the above-mentioned molecules may optionally also be substituted by C1- to C6-alkyl, C1- to C6-alkenyl, CN, NR12, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3 or SO2NR12 or substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle, where R1 has an above-mentioned meaning.
The substituents R3 to R13 are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R3 and R4, R6 and R7, R8 and R9, R10 and R11 and R12 and R13 in compounds of the formulae (7) and (8) may be identical or different. R3 to R13 are particularly preferably each, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, phenyl or cyclohexyl, very particularly preferably methyl, ethyl, n-propyl, isopropyl or n-butyl.
In accordance with the invention, suitable substituents R1′ to R4′ of compounds of the formula (9), besides H, are preferably: C1- to C20, in particular C1- to C12-alkyl groups, and saturated or unsaturated, i.e. also aromatic, C3- to C7-cycloalkyl groups, which may be substituted by C1- to C6-alkyl groups, in particular phenyl.
The substituents R1′ and R4′ are each, independently of one another, particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. They are very particularly preferably methyl, ethyl, n-butyl or hexyl. In pyrrolidine, piperidine, indoline, pyrrolidinium, piperidinium or indolinium compounds, the two substituents R1′ and R4′ are preferably different.
The substituent R2′ or R3′ is in each case, independently of one another, in particular H, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl or benzyl. R2′ is particularly preferably H, methyl, ethyl, isopropyl, propyl, butyl or sec-butyl. R2′ and R3′ are very particularly preferably H.
The C1-C12-alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore also pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Optionally difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.
In accordance with the invention suitable substituents R14 and R15 of the compounds of the formulae (10) and (11), besides H, are preferably: C1- to C20—, particularly preferably C1- to C14-alkyl groups and very particularly preferably C1- to C4-alkyl groups, which may in each case be unbranched or branched and where one or more radicals R14 may be substituted by —NR1*2.
The substituents —R14 and —CH2—R15 here may be identical or different. In a preferred embodiment, all three substituents —R14 and —CH2—R15 are identical. In a further preferred embodiment, two of the substituents —R14 and —CH2—R15 are identical.
The substituents R14 are particularly preferably H, methyl, ethyl, isopropyl or dimethylaminomethyl.
The substituents R15 are particularly preferably H or methyl.
The compound of the formula (11) is preferably selected from the compounds of the formula N(CH3)3, N(C2H5)3, HN(C2H5)2, (CH3)2N—CH2—N(CH3)2 or CH3N((CH(CH3)2)2.
A straight-chain or branched alkenyl having 2 to 20 C atoms, where, in addition, a plurality of double bonds may be present, is, for example, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, —C9H17, —C10H19 to —C20H39; preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, preference is furthermore given to 4-pentenyl, isopentenyl or hexenyl.
A straight-chain or branched alkynyl having 2 to 20 C atoms, where, in addition, a plurality of triple bonds may be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, heptynyl, octynyl, —C9H15, —C10H17 to —C20H37, preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.
Aryl-C1-C6-alkyl denotes, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and also the alkylene chain may be partially or fully substituted, as described above, by halogens, in particular —F and/or —Cl, or partially substituted by —OR1, —NR12, —CN, —C(O)NR12, —SO2NR12.
Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, phenyl, cycloheptenyl, each of which may be substituted by C1- to C6-alkyl groups, where the cycloalkyl group or the cycloalkyl group which is substituted by C1- to C6-alkyl groups may in turn also be substituted by halogen atoms, such as F, Cl, Br or I, in particular F or Cl, or by —OR1, —CN, —C(O)NR12, —SO2NR12.
In the substituents R, R2 to R13 or R1′ to R4′, one or two non-adjacent carbon atoms which are not bonded in the α-position to the heteroatom may also be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, or —P(O)R1—, where R1=non-, partially or perfluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl.
Without restricting generality, examples of substituents R, R2 to R13 and R1′ to R4′ modified in this way are: —OCH3, —OCH(CH3)2, —CH2OCH3, —CH2—CH2—O—CH3, —C2H4OCH(CH3)2, —C2H4SC2H5, —C2H4SCH(CH3)2, —S(O)CH3, —SO2CH3, —SO2C6H5, —SO2C3H7, —SO2CH(CH3)2, —SO2CH2CF3, —CH2SO2CH3, —O—C4H8—)—C4H9, —CF3, —C2F5, —C3F7, —C4F9, —C(CF3)3, —CF2SO2CF3, —C2F4N(C2F5)C2F5, —CHF2, —CH2CF3, —C2F2H3, —C3FH6, —CH2C3F7, —C(CFH2)3, —CH2C6H5 or P(O)(C2H5)2.
In R1, C3- to C7-cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
In R1, substituted phenyl means phenyl which is substituted by C1- to C6-alkyl, C1- to C6-alkenyl, CN, NR12, F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3 or SO2NR*2, where R* denotes a non-, partially or perfluorinated C1- to C6-alkyl or C3- to C7-cycloalkyl, as defined for R1, for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-, p-(trifluoromethyl)phenyl, o-, m-, p-(trifluoromethoxy)phenyl, o-, m-, p-(trifluoromethylsulfonyl)phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodophenyl, further preferably 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dihydroxyphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-difluorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichloro-phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dibromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl or 2,4,5-trimethylphenyl.
In R1′ to R4′, heteroaryl is taken to mean a saturated or unsaturated mono- or bicyclic heterocyclic radical having 5 to 13 ring members, where 1, 2 or 3 N and/or 1 or 2 S or O atoms may be present and the heterocyclic radical may be mono- or polysubstituted by C1- to C6-alkyl, C1- to C6-alkenyl, CN, NR12,F, Cl, Br, I, C1-C6-alkoxy, SCF3, SO2CF3 or SO2NR12, where R1 has a meaning indicated above.
The heterocyclic radical is preferably substituted or unsubstituted 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, furthermore preferably 1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -4- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 2-, 3-, 4-, 5- or 6-2H-thiopyranyl, 2-, 3- or 4-4H-thiopyranyl, 3- or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6- or 7-benzofuryl, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-1H-indolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or 7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or 7-benz-2,1,3-oxadiazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl or 1-, 2- or 3-pyrrolidinyl.
Heteroaryl-C1-C6-alkyl is, analogously to aryl-C1-C6-alkyl, now taken to mean, for example, pyridinylmethyl, pyridinylethyl, pyridinylpropyl, pyridinylbutyl, pyridinylpentyl, pyridinylhexyl, where, furthermore, the heterocycles described above may be linked to the alkylene chain in this way.
HetN+ is preferably




where the substituents R1′ to R4′ each, independently of one another, have a meaning described above.
The organic cation [Kt]x+ is particularly preferably selected from the group comprising imidazolium, pyridinium, pyrrolidinium, ammonium, phosphonium or iminium cations, as defined above.
Particularly suitable imidazolium, pyrrolidinium and ammonium cations are selected from the group tetraalkylammonium, 1,1-dialkylpyrrolidinium, 1-alkyl-1-alkoxyalkylpyrrolidnium or 1,3-dialkylimidazolium, where the alkyl groups or the alkoxy group in the alkoxyalkyl group may each, independently of one another, have 1 to 10 C atoms. Very particularly preferably, the alkly groups have 1 to 6 C atoms and the alkoxy group has 1 to 3 C atoms. The alkyl groups in tetraalkylammonium can therefore be identical or different. Preferably, three alkyl groups are identical and one alkyl group is different or two alkyl groups are identical and the other two are different. Preferred tetraalkylammonium cations are, for example, trimethyl(ethyl)ammonium, triethyl(methyl)ammonium, tripropyl(methyl)ammonium, tributyl(methyl)ammonium, tripentyl(methyl)ammonium, trihexyl(methyl)ammonium, triheptyl(methyl)ammonium, trioctyl(methyl)ammonium, trinonyl(methyl)ammonium, tridecyl(methyl)ammonium, trihexyl(ethyl)ammonium, ethyl(trioctyl)ammonium, propyl(dimethyl)ethylammonium, butyl(dimethyl)-ethylammonium, methoxyethyl(dimethyl)ethylammonium, methoxyethyl(diethyl)methylammonium, methoxyethyl(dimethyl)propylammonium, ethoxyethyl(dimethyl)ethylammonium. Particularly preferred quaternary ammonium cations are propyl(dimethyl)ethylammonium and/or methoxyethyl(dimethyl)ethylammonium.
Preferred 1,1-dialkylpyrrolidinium cations are, for example, 1,1-dimethylpyrrolidinium, 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-methyl-1-butylpyrrolidinium, 1-methyl-1-pentylpyrrolidinium, 1-methyl-1-hexylpyrrolidinium, 1-methyl-1-heptylpyrrolidinium, 1-methyl-1-octylpyrrolidinium, 1-methyl-1-nonylpyrrolidinium, 1-methyl-1-decylpyrrolidinium, 1,1-diethylpyrrolidinium, 1-ethyl-1-propylpyrrolidinium, 1-ethyl-1-butylpyrrolidinium, 1-ethyl-1-pentylpyrrolidinium, 1-ethyl-1-hexylpyrrolidinium, 1-ethyl-1-heptylpyrrolidinium, 1-ethyl-1-octylpyrrolidinium, 1-ethyl-1-nonylpyrrolidinium, 1-ethyl-1-decylpyrrolidinium, 1,1-dipropylpyrrolidinium, 1-propyl-1-methylpyrrolidinium, 1-propyl-1-butylpyrrolidinium, 1-propyl-1-pentylpyrrolidinium, 1-propyl-1-hexylpyrrolidinium, 1-propyl-1-heptylpyrrolidinium, 1-propyl-1-octylpyrrolidinium, 1-propyl-1-nonylpyrrolidinium, 1-propyl-1-decylpyrrolidinium, 1,1-dibutylpyrrolidinium, 1-butyl-1-methylpyrrolidinium, 1-butyl-1-pentylpyrrolidinium, 1-butyl-1-hexylpyrrolidinium, 1-butyl-1-heptylpyrrolidinium, 1-butyl-1-octylpyrrolidinium, 1-butyl-1-nonylpyrrolidinium, 1-butyl-1-decylpyrrolidinium, 1,1-dipentylpyrrolidinium, 1-pentyl-1-hexylpyrrolidinium, 1-pentyl-1-heptylpyrrolidinium, 1-pentyl-1-octylpyrrolidinium, 1-pentyl-1-nonylpyrrolidinium, 1-pentyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptylpyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-dihexylpyrrolidinium, 1-hexyl-1-heptylpyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-hexyl-1-nonylpyrrolidinium, 1-hexyl-1-decylpyrrolidinium, 1,1-diheptylpyrrolidinium, 1-heptyl-1-octylpyrrolidinium, 1-heptyl-1-nonylpyrrolidinium, 1-heptyl-1-decylpyrrolidinium, 1,1-dioctylpyrrolidinium, 1-octyl-1-nonylpyrrolidinium, 1-octyl-1-decylpyrrolidinium, 1-1-dinonylpyrrolidinium, 1-nony-1-decylpyrrolidinium or 1,1-didecylpyrrolidinium. Very particular preference is given to 1-butyl-1-methylpyrrolidinium or 1-propyl-1-methylpyrrolidinium.
Preferred 1-alkyl-1-alkoxyalkylpyrrolidinium cations are, for example, 1-methoxyethyl-1-methylpyrrolidinium, 1-methoxyethyl-1-ethylpyrrolidinium, 1-methoxyethyl-1-propylpyrrolidinium, 1-methoxyethyl-1-butylpyrrolidinium, 1-ethoxyethyl-1-methylpyrrolidinium, 1-ethoxymethyl-1-methylpyrrolidinium. Very particular preference is given to 1-methoxyethyl-1-methylpyrrolidinium.
Preferred 1,3-dialkylimidazolium cations are, for example, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-3-pentylimidazolium, 1-ethyl-3-propylimidazolium, 1-butyl-3-ethylimidazolium, 1-ethyl-3-pentylimidazolium, 1-butyl-3-propylimidazolium, 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1,3-dipropypylimidazolium, 1,3-dibutylimidazolium, 1,3-dipentylimidazolium, 1,3-dihexylimidazolium, 1,3-diheptylimidazolium, 1,3-dioctylimidazolium, 1,3-dinonylimidazolium, 1,3-didecylimidazolium, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-methyl-3-nonylimidazolium, 1-decyl-3-methylimidazolium, 1-ethyl-3-hexylimidazolium, 1-ethyl-3-heptylimidazolium, 1-ethyl-3-octylimidazolium, 1-ethyl-3-nonylimidazolium or 1-decyl-3-ethylimidazolium. Particularly preferred cations are 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium or 1-methyl-3-propylimidazolium.
The organic cation [Kt]x+ is very particularly preferably a cation selected from the group comprising 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium.
In formula (3) of the process according to the invention, [X]− stands for a hydrophilic anion. This is preferably an anion selected from the group comprising Cl−, Br−, I−, sulfate, sulfonate, acetate and BF4−.
A further very particularly preferred embodiment of the present invention is a process for the preparation of a compound of the formula (1) as defined above in which [Kt]x+ is an iminium cation, where a compound of the formula (2) as defined above is reacted with a tertiary or secondary amine of the formula (11) as defined above. This embodiment has the advantage that a compound of the formula (1) containing the organic iminium cation can be prepared directly in one step without a subsequent metathesis reaction being necessary in a second step. The following reaction scheme illustrates this reaction by way of example:




The iminium salts formed here are very reactive compounds.
For example, these compounds are intermediates in the Vilsmeier-Haack reaction, Ugi reaction, Houben-Hoesch reaction, Duff reaction and Stephen aldehyde synthesis. Iminium salts are, in addition, useful starting compounds for the synthesis of β-oxocarboxylic acid esters and β-diketones [Organikum [Practical Organic Chemistry], WILEY-VCH, 2001, p. 617] or for the synthesis of pyrrolidinium derivatives via a Cope rearrangement and intramolecular Mannich reaction [L. E. Overmann, Acc. Chem. Res., 25 (1992), p. 352-359]. Iminium salts react with alcohols (alcoholates), amines, Grignard reagents, alkyl- and aryllithium compounds, compounds containing active methyl(CH2) groups, diazoalkanes (for example CH2N2) or 1,3-dienes.
Iminium salts are frequently used in the synthesis of amino compounds, quaternary ammonium salts, aldehydes, ketones, heterocyclic compounds or steroids [Chemical Encyclopaedia (Russ.) Vol 2, p. 418-419, Moscow, 1990].
More recent publications [T. Yamaguchi, et al., Chem and Ind., 1972, p. 380; J. of the Am. Chem. Soc., 126 (2004), p. 5968; J. of the Am. Chem. Soc., 128 (2006), p. 5648; J. of the Am. Chem. Soc., 129 (2007), p. 780; J. of the Am. Chem. Soc., 130 (2008), p. 11005; Tetrahedron, 62 (2006), p. 6312; Org. Letters, 6 (2006), p. 4093; Org. Letters, 10 (2008), p. 1417; Acc. Chem. Res., 42 (2009), p. 335; Angew. Chem. Int. Ed., 49 (2010), p. 3037] show the broad range of applications of iminium salts. The direct synthesis of these salts from tertiary or secondary amines therefore furthermore enables improvement and simplification of the preparation of a multiplicity of compounds.
Thus, for example, intermolecular rearrangements can occur starting from the iminium salts of the formula (1), where [Kt]x+ is an iminium cation, obtained in the process according to the invention. Alternatively, the iminium salts can also react further spontaneously with the nucleophilic reagents, which is depicted by way of example in the following reaction scheme:




In accordance with the invention, the reaction in the first step of the process according to the invention can be carried out at −80 to 50° C. The reaction in the first step is preferably carried out at −20 to 25° C. A temperature of 0° C. is particularly preferred.
The choice of a suitable temperature for the reaction is of particular importance here in order that, in contrast to the reaction disclosed in WO 03/087113, no reduction of the substrate occurs, but instead the addition of a hydride ion takes place.
The reaction in the second step of the process according to the invention is preferably carried out at room temperature.
The reaction in the first step of the process according to the invention is preferably carried out in an aprotic solvent, such as, for example, dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, hexane, cyclohexane, benzene, dichloromethane or dichloroethane. Cyclic or linear ethers, such as tetrahydrofuran, diethyl ether or methyl tert-butyl ether, are particularly preferably employed. The solvent is very particularly preferably tetrahydrofuran.
The reaction in the second step of the process according to the invention is preferably carried out in water or in a mixture of water and organic solvent.
With the aid of the process according to the invention, various salts having (perfluoroalkyl)fluorohydrogenphosphate anions can be prepared in a simple and comfortable manner. The following reaction scheme illustrates the first step of the process according to the invention with reference to the reaction of (perfluoroalkyl)fluorophosphoranes with, for example, LiAlH4 as hydride ion donor:




The lithium salt obtained in this way, lithium (perfluoroalkyl)fluorohydrogenphosphate (Li[(CnF2n+1)zPF5-zH]), is not only of interest for use as conductive salt (such as, for example, in Li ion batteries or in supercapacitors), but can also be used as starting material for the synthesis of various salts having organic cations (ionic liquids). This reaction represents the second step of the process according to the invention and is illustrated below by way of example:




The present invention therefore likewise relates to the use of a compound of the formula (1) in which [Kt]+ is an inorganic cation for the preparation of a compound of the formula (1) in which [Kt]+ is an organic cation.
For example, ionic liquids can be prepared in this way.
The compounds of the formula (1) in which [Kt]+ is an organic cation which have been prepared with the aid of the process according to the invention have a multiplicity of applications:
Thus, owing to their purity, the absent vapour pressure and the high stability as solvent or solvent additive, they are suitable in chemical reactions. The use as solvent additive takes place in combination with other solvents. Furthermore, the ionic liquids according to the invention can be employed as phase-transfer catalysts, heat-exchange media, as surface-active substances, plasticisers, flameproofing agents or as conductive salts. In addition, the ionic liquids according to the invention are suitable as extractants in substance separation processes.
Owing to their electrochemical properties, the ionic liquids according to the invention can be employed, in particular, in electrochemical applications, such as, for example, as electrolyte in batteries, sensors, accumulators, capacitors or as constituent of a solar cell (solvent and/or electrolyte), preferably a dye solar cell or a sensor.
The ionic liquids prepared with the aid of the process according to the invention have modified properties, such as, for example, modified stability, compared with known ionic liquids.
These hydrophobic ionic liquids can be converted (optionally by heating) into hydrophilic ionic liquids having bis(perfluoroalkyl)phosphinate ((CnF2n+1)2P(O)O−) or perfluoroalkylphosphonate anion ((CnF2n+1)P(O)O2−2) using water or caustic lye solution:




Owing to these unusual properties of the compounds according to the invention, different compounds having certain properties can be prepared as required, for example for use in extraction methods. An in situ conversion of hydrophobic ionic liquids into hydrophilic ionic liquids enables the development of a simple isolation method of water-insoluble products subsequent to a synthesis in hydrophobic ionic liquids having (perfluoroalkyl)fluorohydrogenphosphate anion.
A further difference of ionic liquids having (perfluoroalkyl)fluorohydrogenphosphate anions from other ionic liquids is their reduced stability. This can be attributed to the fact that the symmetry of the (perfluoroalkyl)fluorohydrogenphosphate anions is increased compared with the FAP anion. On hydrolysis, bis(perfluoroalkyl)phosphinates or perfluoroalkylphosphonates form, as already depicted with reference to Scheme 3. On continued hydrolysis, phosphates are formed, as depicted below:




Natural products in the form of phosphates (calcium phosphate is usually formed in the environment) are thus ultimately obtained.
The present invention furthermore relates to compounds of the formula (1)

[Kt]x+[(CnF2n+1)zPF5-zH]−x  (1)

in which [Kt]x+ is an inorganic or organic cation,
where n=1-8, x=1-4 and z=1-4,
where the compounds [(CF3)2PF3H]−K+, [(CF3)2PF3H]−[(CH3)2NH2]+, [(CF3)PF4H]−K+ and [(CF3)PF4H]−[(CH3)2NH2]+ are excluded.
The cation [Kt]x+ of the compounds of the formula (1) according to the invention can stand for an organic or inorganic cation.
In the case of an inorganic cation, this is preferably a metal cation. Particular preference is given to an alkali-metal cation, preferably a lithium, potassium or sodium cation.
Compounds according to the invention having an inorganic cation are particularly suitable as starting materials for the synthesis of compounds according to the invention having organic cations, so-called ionic liquids, as described above.
Particular preference is therefore given to compounds of the formula (1) in which [Kt]x+ is an organic cation.
The organic cation is preferably selected from the group comprising ammonium, phosphonium, uronium, thiouronium, sulfonium, oxonium, guanidinium cations, heterocyclic cations and iminium cations, which are defined as described above.
[Kt]x+ of the compound of the formula (1) according to the invention is particularly preferably an organic cation which is selected from the group comprising imidazolium, pyridinium, pyrrolidinium, ammonium, phosphonium, sulfonium and iminium cations, as defined above.
The organic cations [Kt]x+ are very particularly preferably a cation selected from the group comprising phenylphosphonium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, N-hexylpyridinium and 1-butyl-2,3-dimethylimidazolium.
z in the compounds of the formula (1) according to the invention preferably stands for 2 or 3; z is particularly preferably =3.
In addition, n in formula (1) preferably stands for 2, 3 or 4, particularly preferably for 2 or 4. n very particularly preferably stands for 2.
The compounds of the formula (1) are particularly preferably selected from [Kt]x+[(C2F5)3PF2H]−x or [Kt]x+[(C2F5)2PF3H]−x, in which [Kt]x+ stands for an organic cation selected from the group comprising ammonium, phosphonium, uronium, thiouronium, sulfonium, oxonium, guanidinium cations and heterocyclic cations, as defined above; the compounds are preferably selected from tetraphenylphosphonium difluorohydridotris(pentafluoroethyl)-phosphate, 1-ethyl-3-methylimidazolium difluorohydridotris(pentafluoroethyl)phosphate, 1-butyl-3-methylimidazolium difluorohydridotris(pentafluoroethyl)phosphate, N-hexylpyrridinium difluorohydridotris(pentafluoroethyl)phosphate, N-butyl-N-methylpyrrolidinium difluorohydridotris(pentafluoroethyl)phosphate and 1-butyl-2,3-dimethylimidazolium difluorohydridotris(pentafluoroethyl)phosphate.
As described above, the compounds according to the invention have many different properties which facilitate their use in various areas of application.
The following working examples are intended to explain the invention without limiting it. The invention can be carried out correspondingly throughout the entire range claimed. Possible variants can also be derived starting from the examples. In particular, the features and conditions of the reactions described in the examples can also be applied to other reactions which are not shown in detail, but fall within the scope of protection of the claims.


EXAMPLES
Example 1
Tetraphenylphosphonium difluorohydridotris(pentafluoroethyl)phosphate




2.38 g (5.4 mmol) of (C2F5)3PF2 are slowly added at 0° C. to 5.6 ml of a one molar LiAlH4/THF solution (5.6 mmol), and the mixture is stirred for 20 minutes. The solution is hydrolysed at 0° C. using water, giving a colourless precipitate (aluminium hydroxide), and 1.89 g (5.1 mmol) of [PPh4]Cl in 5 ml of chloroform are added. The precipitate is filtered off and washed with chloroform. The aqueous phase is separated off, and the chloroform phase is dried in vacuo, leaving a colourless precipitate.
Yield (based on [PPh4]Cl): 3.18 g (78%)
Melting point: 114-116° C.







TABLE 1.1







19F-NMR data of [PPh4][P(C2F5)3F2H] in CDCl3











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














−81.4
m
—
trans-CF3
1.6


−83.1
m
—
cis-CF3
3.3


−113.9
d, d, m
1J(PF) = 737
PF
1




2J(FH) = 58


−120.6
d, m
2J(PF) = 104
trans-CF2
1


−127.3
d, m
2J(PF) = 93
cis-CF2
2
















TABLE 1.2







31P-NMR data of [PPh4][P(C2F5)3F2H] in CDCl3











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














23.4
s
—
[PPh4][(C2F5)3PF2H]
1


−154.9
d, t, quin, t
1J(PF) = 738
[PPh4][(C2F5)3PF2H]
0.9




2J(PFtrans) = 104




2J(PFcis) = 93




1J(PH) = 678
















TABLE 1.3







1H-NMR data of [PPh4][P(C2F5)3F2H] in CDCl3











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














5.6
d, t, t, m
1J(PH) = 678
[(C2F5)3PF2H]−
1




2J(HF) = 64




3J(HFtrans) = 13


7.6-7.9
m
—
[P(C6H5)4]+
25
















TABLE 1.4







Elemental analysis data










C
H















calculated
47.01
2.76



experimental
47.15
2.87

















TABLE 1.5







Mass-spectrometric data (EI, 20 eV)











m/e
Rel. intensity [%]
Assignment















672
1
[PPh3(C2F5)3PFH]+



628
0
[PPh4(C2F5)2PH]+



596
2
[PPh4(C2F5)(CF3)PF2]+



566
1
[PPh3(C2F5)2PF2]+



551
0
[PPh3(C2F5)2PH]+



520
2
[PPh3(C2F5)(CF3)PF2]+



490
4
[PPh2(C2F5)2PF2]+



444
2
[PPh(C2F5)(CF3)PF2]+



414
13
[PPh(C2F5)2PF2]+



355
6
[PPh2(C2F5)PF]+



337
53
[PPh4]+



277
7
[PPh(C2F5)PF]+



262
100
[PPh3]+



183
23
[(C2F5)PFH]+



108
7
[PPh]+



78
9
[Ph]+

















TABLE 1.6







ESI mass spectrum - negative scan mode











Signal
Rel. intensity [%]
Assignment















307.18
19
[(C2F5)2PF2]−



417.21
100
[(C2F5)3PF2H]−










Example 2
1-Ethyl-3-methylimidazolium difluorohydridotris-(penta-fluoroethyl)phosphate, [EMIM][P(C2F5)3F2H]




8.1 g (19 mmol) of (C2F5)3PF2 are slowly added at 0° C. to 20 ml of a one molar LiAlH4/THF solution (20 mmol), and the mixture is stirred for 30 minutes. The solution is hydrolysed using water at 0° C., giving a colourless precipitate (aluminium hydroxide), and 2.8 g (19 mmol) of 1-ethyl-3-methylimidazolium chloride, dissolved in 2 ml of water, are added. After stirring for 30 minutes, the precipitate is filtered off. A second phase deposits, which is separated off and extracted twice with water. It is subsequently dried in vacuo, leaving a colourless liquid.
Yield (based on 1-ethyl-3-methylimidazolium chloride): 3.4 g (33%)
Analytical data of [EMIM][P(C2F5)3F2H]:
















Melting point [° C.]
−2.4



Decomposition [° C.]
176



H2O content [ppm]
43



Cl− content [ppm]
<5



F− content [ppm]
112

















TABLE 2.1







19F-NMR data of [EMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














−81.1
m, d
4J(FH) = 1
trans-CF3
1


−82.3
quin, d
3J(PF) = 9
cis-CF3
2




4J(FH) = 2


−114.1
d, d, m
1J(PF) = 736
PF
0.7




2J(FH) = 64


−119.7
d, m
2(PF) = 104
trans-CF2
0.6


−126.3
d, m
2J(PF) = 93
cis-CF2
1.2
















TABLE 2.2







31P-NMR data of [EMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment





−154.4
d, t, quin, t
1J(PF) = 735
[C2F5)3PF2H]−




1J(PH) = 678




2J(PFtrans) = 104




2J(PFcis) = 93
















TABLE 2.3







1H-NMR data of [EMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral





1.6
t
3J(HH) = 7
H7
3


4.0
s
—
H8
3


4.4
q
3J(HH) = 7
H6
2


5.7
d, t, t, m
1J(PH) = 675
[(C2F5)3PF2H]−
1




2J(HF) = 63




3J(HFtrans) = 13


7.7/7.8
t
3J(HH) = 2
H4/5
2


9.0
s
—
H2
1
















TABLE 2.4







13C{1H}-NMR data of [EMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment













14.5
s
—
C7


35.6
s
—
C8


44.9
s
—
C6


119.9
m
—
—CF2CF3


122.2
s
—
C5


122.9
m
—
—CF2CF3


123.9
s
—
C4


136.2
s
—
C2





a{1H}


b{19F}






Example 3
1-Butyl-3-methylimidazolium difluorohydridotris(pentafluoroethyl)phosphate, [BMIM][P(C2F5)3F2H]




12.1 g (28.5 mmol) of (C2F5)3PF2 are slowly added at 0° C. to 30 ml of a one molar LiAlH4/THF solution (30 mmol), and the mixture is stirred for 30 minutes. The solution is hydrolysed using water at 0° C., giving a colourless precipitate (aluminium hydroxide), and 4.9 g (28.5 mmol) of 1-butyl-3-methylimidazolium chloride in water are added. After stirring for 20 minutes, the precipitate is filtered off. A second phase deposits, which is separated off and extracted twice with water. It is subsequently dried in vacuo, leaving a colourless viscous liquid.
Yield (based on 1-butyl-3-methylimidazolium chloride): 10.2 g (64%)
Analytical data of [BMIM][P(C2F5)3F2H]:
















Glass transition [° C.]
−86



Cold crystallisation [° C.]
−38



Melting point [° C.]
−2.6



Decomposition [° C.]
177



H2O content [ppm]
40



Cl− content [ppm]
<5



F− content [ppm]
48










Viscosity and density of [BMIM][P(C2F5)3F2H]:












T [° C.]
ν [mm2/s]
ρ [g/cm3]







20
96.48
1.581


30
58.94
1.571


40
38.64
1.560


50
26.78
1.549


60
19.45
1.538


70
14.65
1.527


80
11.38
1.517
















TABLE 3.1







19F-NMR data of [BMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














−80.8
m
—
trans-CF3
1


−81.9
m
—
cis-CF3
1.9


−115.0
d, d, m
1J(PF) = 724
PF
0.6




2J(FH) = 65


−119.1
d, m
2J(PF) = 107
trans-CF2
0.6


−125.7
d, m
2J(PF) = 92
cis-CF2
1.3
















TABLE 3.2







31P-NMR data of [BMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment





−154.2
d, t, quin, t
1J(PF) = 737
[C2F5)3PF2H]−




1J(PH) = 676




2J(PFtrans) = 104




2J(PFcis) = 94
















TABLE 3.3







1H-NMR data of [BMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














0.9
t
3J(HH) = 7
H9
3.1


1.4
sext
3J(HH) = 8
H8
2.1


1.9
quin
3J(HH) = 7
H7
2.2


4.0
s
—
H10
3.1


4.4
t
3J(HH) = 8
H6
2


5.7
d, t, t, m
1J(PH) = 675
[(C2F5)3PF2H]−
0.6




2J(HF) = 63




3J(HFtrans) = 13


7.7
m
3J(HH) = 7
H4, H5
2


9.1
s
—
H2
1
















TABLE 3.4







13C{1H}-NMR data of [BMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment













12.7
s
—
C9


19.0
s
—
C8


31.8
s
—
C7


35.7
s
—
C6


49.4
s
—
C10


118.9
m
—
—CF2CF3


122.5
s
—
C4


122.9
m
—
—CF2CF3


123.9
s
—
C5


136.4
s
—
C2





a{1H}


b{19F}






Example 4
N-Hexylpyrridinium difluorohydridotris(pentafluoroethyl)phosphate, [HPy][P(C2F5)3F2H]




12.14 g (28.5 mmol) of (C2F5)3PF2 are slowly added at 0° C. to 30 ml of a one molar LiAlH4/THF solution (30 mmol), and the mixture is stirred for 30 minutes. The solution is hydrolysed using water at 0° C., giving a colourless precipitate (aluminium hydroxide), and 5.67 g (28.5 mmol) of N-hexylpyrridinium chloride, dissolved in 10 ml of water, are added. After stirring for 30 minutes, the precipitate is filtered off. The emulsion obtained is dried in vacuo. The cloudy, viscous residue is extracted three times with water and again dried in vacuo, leaving a colourless liquid.
Yield (based on N-hexylpyrridinium chloride): 9.98 g (59%)
Analytical data of [HPy][P(C2F5)3F2H]
















Glass transition [° C.]
−76



Decomposition [° C.]
166



H2O content [ppm]
27



Cl− content [ppm]
143

















TABLE 4.1







19F-NMR data of [HPy][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














−79.9
m
—
trans-CF3
1


−81.1
m
—
cis-CF3
2


−112.9
d, d, m
1J(PF) = 737
PF
0.6




2J(FH) = 61


−118.6
d, m
2J(PF) = 105
trans-CF2
0.5


−125.2
d, m
2J(PF) = 92
cis-CF2
1.2
















TABLE 4.2







31P-NMR data of [HPy][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment





−152.7
d, t, quin, t
1J(PF) = 737
[C2F5)3PF2H]−




1J(PH) = 676




2J(PFtrans) = 104




2J(PFcis) = 94
















TABLE 4.3







1H-NMR data of [HPy][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral





0.9
m

H12
3


1.3; 1.9
m

H8-H11
9


4.5
t
3J(HH) = 7
H7
2


5.6
d, t, t, m
1J(PH) = 673
[(C2F5)3PF2H]−
1




2J(HF) = 63




3J(HFtrans) = 13


8.0
m
—
H3, H5
2


8.5
t
3J(HH) = 8
H4
1


8.7
d
3J(HH) = 6
H2, H6
2
















TABLE 4.4







13C-{1H}-NMR data of [HPy][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment













13.1
s
—
C12


22.0
s
—
C11


25.2
s
—
C10


30.7
s
—
C9


30.8
s
—
C8


61.9
s
—
C7


118.2
m
—
—CF2CF3


120.9
m
—
—CF2CF3


128.4
s
—
C4


144.4
s
—
C3, C5


145.7
s
—
C2, C6





a{1H}


b{19F}






Example 5
1-Butyl-2,3-dimethylimidazolium difluorohydridotris(pentafluoroethyl)phosphate, [BMMIM][P(C2F5)3F2H]




12.1 g (28.5 mmol) of (C2F5)3PF2 are slowly added at 0° C. to 30 ml of a one molar LiAlH4/THF solution (30 mmol), and the mixture is stirred for 30 minutes. The solution is hydrolysed using water at 0° C., giving a colourless precipitate (aluminium hydroxide), and 5.4 g (28.5 mmol) of 1-butyl-2,3-dimethylimidazolium chloride, dissolved in 2 ml of water, are added. After stirring for 20 minutes, the precipitate is filtered off. A second phase deposits, which is separated off and extracted twice with water. It is subsequently dried in vacuo, leaving a colourless liquid.
Yield (based on 1-butyl-2,3-dimethylimidazolium chloride): 9.1 g (55%)
Analytical data of [BMMIM][P(C2F5)3F2H]:
















Glass transition [° C.]
−78



Cold crystallisation [° C.]
−24



Melting point [° C.]
9.6



Decomposition [° C.]
179



H2O content [ppm]
122



Cl− content [ppm]
6



F− content [ppm]
198

















TABLE 5.1







19F-NMR data of [BMMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














−79.9
m
—
trans-CF3
1


−81.1
m
—
cis-CF3
2


−112.9
d, d, m
1J(PF) = 737
PF
0.7




2J(FH) = 65


−118.6
d, m
2J(PF) = 105
trans-CF2
0.6


−125.1
d, m
2J(PF) = 95
cis-CF2
1.2
















TABLE 5.2







31P-NMR data of [BMMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment





−153.7
d, t, quin, t
1J(PF) = 737
[C2F5)3PF2H]−




1J(PH) = 674




2J(PFtrans) = 104




2J(PFcis) = 92
















TABLE 5.3







1H-NMR data of [BMMIM][P(C2F5)3F2H] in acetone-d6











δ [ppm]
Multiplicity
J [Hz]
Assignment
Integral














1.0
t
3J(HH) = 7
H9
1.5


1.4
sext
3J(HH) = 7
H8
1


1.9
quin
3J(HH) = 7
H7
1


2.8
s
—
H11
1.5


3.9
s
—
H10
1.6


4.3
t
3J(HH) = 7
H6
1.1


5.7
d, t, t, m
1J(PH) = 675
[(C2F5)3PF2H]−
—




2J(HF) = 63




3J(HFtrans) = 13


7.6
m
—
H4, H5
1
















TABLE 5.4







13C-{1H}-NMR data of [BMMIM][P(C2F5)3F2H] in acetone-d6










δ [ppm]
Multiplicity
J [Hz]
Assignment













8.9
s
—
C11


12.7
s
—
C9


19.1
s
—
C8


31.2
s
—
C7


34.6
s
—
C10


48.0
s
—
C6


120.8
s

C4/5


122.2
s
—
C4/5


144.4
s
—
C2









Example 6
Hydrolysis of [EMIm][P(C2F5)3F2H]




0.72 g of [EMIm][P(C2F5)3PF2H] are stirred at 110° C. for 8 hours in 10 ml of H2O. Volatile constituents are subsequently removed in vacuo, and the residue is investigated by NMR spectroscopy.







TABLE 6.1







31P-NMR spectroscopic data of the residue in H2O










δ [ppm]
Multiplicity
J[Hz]
Assignment













5.4
d, t
1J(PH) = 586
(C2F5)PH(O)OH




2J(PF) = 80


2.3
quin
2J(PF) = 76
(C2F5)2P(O)OH


−3.5
t
2J(PF) = 78
(C2F5)P(O)(OH)2









Example 7
Synthesis of [Me2NCH2NMe3][P(C2F5)3F2H]




0.43 g (7.3 mmol) of trimethylamine, NMe3, are condensed into 5.14 g (12.1 mmol) of tris(pentafluoethyl)difluorophosphorane, (C2F5)3PF2. The mixture is brought to room temperature, whereupon two phases can be observed. The mixture is subsequently stirred at room temperature for 24 hours. After a few hours, a colourless solid forms. After one day, volatile substances are removed in vacuo, leaving a colourless solid. Yield of the crude product (based on NMe3) is virtually quantitative (1.99 g).







TABLE 7.1







31P-NMR data of [(CH3)2NCH2N(CH3)3][P(C2F5)3F2H] in CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





−153.7
d, t, quin, t
1J(PH) = 674
[P(C2F5)3F2H]−




1J(PF) = 733




2J(PFcis) = 94




2J(PFtrans) = 104
















TABLE 7.2







19F-NMR data of [(CH3)2NCH2N(CH3)3][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














−80.6
m
—
trans-CF3
3


−81.8
m
—
cis-CF3
6


−113.6
d, d, m,
1J(PF) = 733
PF
2




2J(FH) = 62


−119.1
d, m
2J(PFtrans) = 104
trans-CF2
2


−125.7
d, m
2J(PFcis) = 94
cis-CF2
4
















TABLE 7.3







1H-NMR spectroscopic data of [(CH3)2NCH2N(CH3)3][P(C2F5)3F2H]


in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral





2.6
s
—
(CH3)2N—
6


2.8
s
—
—N(CH3)3
9


4.0
s
—
—NCH2N—
2


5.7
d, t, m
1J(PH) = 675
[P(C2F5)3PF2H]−
1




2J(FH) = 63
















TABLE 7.4







13C{1H}-NMR spectroscopic data of


[(CH3)2NCH2N(CH3)3][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral





45.3
s
—
(CH3)2N—



48.4
s
—
—N(CH3)3


90.5
s
—
—NCH2N—









Example 8
Reaction of N(C2H5)3 with (C2F5)3PF2




0.92 g (9.07 mmol) of triethylamine, NEt3, are added to 3.77 g (8.85 mmol) of tris(pentafluoethyl)difluorophosphorane, (C2F5)3PF2. The mixture is stirred at room temperature for 24 hours, during which it becomes an intense brown colour and becomes oily with solid components. Volatile constituents are removed in vacuo. Crude yield: 3.94 g. The crude product is dissolved in CH2Cl2, and the product, [(C2H5)3NH]—[P(C2F5)3F2H], is brought to crystallisation at −28° C.
IR(ATR): v(NH) 3203 cm−1







TABLE 8.1







31P-NMR data of [(C2H5)3NH][P(C2F5)3F2H] in CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





−152.6
d, t, quin, t
1J(PH) = 681
[P(C2F5)3F2H]−




1J(PF) = 723




2J(PFtrans) = 107




2J(PFcis) = 92
















TABLE 8.2







19F-NMR data of [(C2H5)3NH][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














−81.0
m
—
trans-CF3
3


−82.2
“quin”, d
8.5/1
cis-CF3
6


−115.3
d, d, m
1J(PF) = 719
[P(C2F5)3F2H]−
2




2J(HF) = 62


−119.2
d, m
2J(PF) = 107
trans-CF2
2


−125.8
d, m
2J(PF) = 95
cis-CF2 ([P(C2F5)3F2H]−)
4
















TABLE 8.3







1H-NMR data of [(C2H5)3NH][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral





1.3
t
3J(HH) = 7
—CH3
9


3.2
quar
3J(HH) = 7
—CH2—
6


5.7
d, quin, t, m
1J(PH) = 645
[P(C2F5)3F2H]−
1




3J(FH) = 13




3J(FH) = 2
















TABLE 8.4







13C{1H}-NMR data of [(C2H5)3NH][P(C2F5)3F2H] in CD3CN












δ, ppm
Multiplicity
J/Hz
Assignment
















8.2
s
—
—CH3



47.0
s
—
—CH2—










Example 9
Reaction of HN(C2H5)2 with (C2F5)3PF2




0.60 g (8.25 mmol) of diethylamine, HNEt2, are added to 3.44 g (8.08 mmol) of tris(pentafluoethyl)difluorophosphorane, (C2F5)3PF2. The mixture is stirred at room temperature for 24 hours, during which it becomes an intense brown colour. Volatile constituents are removed in vacuo. Crude yield: 3.18 g.
The crude product is dissolved in CH2Cl2, and the product, [(C2H5)2NH2]-[P(C2F5)3F2H], is brought to crystallisation at −28° C.







TABLE 9.1







31P-NMR data of [(C2H5)2NH2][P(C2F5)3F2H] in CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





−153.2
d, t, quin, t
1J(PH) = 679
[P(C2F5)3F2H]−




1J(PF) = 721




2J(PFcis) = 92




2J(PFtrans) = 106
















TABLE 9.2







19F-NMR data of [(C2H5)2NH2][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














−81.5
m
—
trans-CF3
—


−82.8
m
—
cis-CF3
—


−114.9
d, d, m
1J(PF) = 722
[P(C2F5)3F2H]−
2




2J(HF) = 65


−119.3
d, m
2J(PFtrans) = 105
trans-CF2
2


−126.0
d, m
2J(PFcis) = 92
cis-CF2
4
















TABLE 9.3







1H-NMR data of [(C2H5)2NH2][P(C2F5)3F2H] in CD2Cl2











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














1.4
t
7
—CH3
1.5


3.1
quar
7
—CH2—
1


5.8
d, t, quin, m
1J(PH) = 681
[P(C2F5)3F2H]−
0.15




2J(HF) = 63




3J(HFcis) = 14
















TABLE 9.4







13C{1H}-NMR data of [(C2H5)2NH2][P(C2F5)3F2H] in CD2Cl2












δ, ppm
Multiplicity
J/Hz
Assignment







10.9
s
—
—CH3



43.6
s
—
—CH2—










Example 10
Reaction of Me2NCH2NMe2 with (C2F5)3PF2




4.5 g (10.6 mmol) of tris(pentafluoethyl)difluorophosphorane, (C2F5)3PF2, are added at room temperature to 0.88 g (8.6 mmol) of Me2NCH2NMe2. Two phases can be observed. The mixture is stirred for 24 hours, during which a yellow emulsion forms. Excess (C2F5)3PF2 is removed in vacuo, and the residue is investigated by NMR spectroscopy.
IR(ATR): v(NH) 3202 cm−1







TABLE 10.1







31P-NMR data of the [P(C2F5)3F2H] anion in CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





−154.1
d, t, quin, m
1J(PH) = 678
[P(C2F5)3F2H]−




1J(PF) = 730




2J(PFcis) = 93
















TABLE 10.2







19F-NMR data of the [P(C2F5)3F2H] anion in CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment













−81.1
m
—
trans-CF3


−82.4
m
—
cis-CF3


−113.2
d, d, m
1J(PF) = 724
[P(C2F5)3F2H]−




2J(HF) = 68


−119.3
d, m
2J(PFtrans) = 118
trans-CF2


−125.7
d, m
2J(PFcis) = 94
cis-CF2









Example 11
Reaction of i-(C3H7)2NCH3 with (C2F5)3PF2




0.82 g (7.12 mmol) of N,N-diisopropylmethylamine are dissolved in 50 ml of diethyl ether, and 3.03 g (7.0 mmol) of tris(pentafluoethyl)difluorophosphorane, (C2F5)3PF2, are added at room temperature. The mixture is stirred for four days and subsequently freed from volatile substances in vacuo, leaving a brown solid, which is purified by recrystallisation from CH2Cl2 at −28° C., leaving a colourless solid. Yield: 2.61 g.







TABLE 11.1







31P-NMR data of [((CH3)2CH)2N(H)CH3][P(C2F5)3F2H] in


CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





−154.4
d, t, quin, t
1J(PH) = 675
[P(C2F5)3F2H]−




1J(PF) = 733




2J(PFtrans) = 104




2J(PFcis) = 94
















TABLE 11.2







19F-NMR data of [((CH3)2CH)2N(H)CH3][P(C2F5)3F2H] in


CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














−81.3
m
—
trans-CF3
3


−82.5
m
—
cis-CF3
6


−114.3
d, d, m
1J(PF) = 734
[P(C2F5)3F2H]−
2




2J(HF) = 63


−119.8
d, m
2J(PFtrans) =
trans-CF2
2




105


−126.5
d, m
2J(PFcis) = 93
cis-CF2
4
















TABLE 11.3







1H-NMR data of [((CH3)2CH)2N(H)CH3][P(C2F5)3F2H] in CD3CN











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














1.5
d
3J(HH) = 7
—CH(CH3)2
1


2.8
s

—NCH3
0.2


3.7
sept
3J(HH) = 7
—CH(CH3)2
0.15


5.7
d, t, quin, m
1J(PH) = 680
[P(C2F5)3F2H]
0.15




2J(HF) = 64




3J(HFcis) = 13
















TABLE 11.4







13C{1H}-NMR data of [((CH3)2CH)2N(H)CH3][P(C2F5)3F2H] in


CD3CN










δ, ppm
Multiplicity
J/Hz
Assignment





19.3
s
—
CH3


32.3
s
—
NCH3


56.8
s
—
NCH









Example 12
Reaction of [Me2NCH2NMe3][P(C2F5)3F2H] with (PhO)2P(O)H


[(CH3)2NCH2N(CH3)3][(C2F5)3PF2H]+(C6H5O)2P(O)H→(CH3)2NCH2P(O)(OC6H5)2+[HN(CH3)3][(C2F5)3PF2H]

[Me2NCH2NMe3][P(C2F5)3F2H] is dissolved in CH2Cl2, and an excess of (PhO)2PHO is added. The solution is investigated by NMR spectroscopy.







TABLE 12.1







31P-NMR data of the products in CH2Cl2










δ, ppm
Multiplicity
J/Hz
Assignment













7.3
t
2J(PCH2) = 13
Me2NCH2P(O)(OPh)2


−153.8
d, t, quin, t
1J(PH) = 678
[P(C2F5)3F2H]−




1J(PF) = 731




2J(PFtrans) = 104




2J(PFcis) = 93
















TABLE 12.2







13C{1H}-NMR data of the products in CH2Cl2










δ, ppm
Multiplicity
J/Hz
Assignment





44.7
s
—
HN(CH3)3+


45.1
d
3J(PC) = 5
(CH3)2NCH2P(O)(OPh)2


51.4
d
1J(PC) = 157
(CH3)2NCH2P(O)(OPh)2









Example 13
Reaction of [Me2NCH2NMe3][P(C2F5)3F2H] with P(CH3)3




[Me2NCH2NMe3][P(C2F5)3F2H] is dissolved in CH2Cl2, and excess P(CH3)3 is condensed on. The solution is investigated by NMR spectroscopy.







TABLE 13.1







31P-NMR data of [(CH3)2NCH2P(CH3)3][P(C2F5)3F2H] in CH2Cl2










δ, ppm
Multiplicity
J/Hz
Assignment













24.3
dec, t
2J(PCH3) = 13
[(CH3)2NCH2P(CH3)3]+




2J(PCH2) = 4




1J(PC) = 54


−154.1
d, t, quin, t
1J(PH) = 678
[P(C2F5)3F2H]−




1J(PF) = 728




2J(PFtrans) = 105




2J(PFcis) = 93
















TABLE 13.2







19F-NMR data of [(CH3)2NCH2P(CH3)3][P(C2F5)3F2H] in CH2Cl2











δ, ppm
Multiplicity
J/Hz
Assignment
Integral














−80.8
m
—
trans-CF3
3


−82.0
m
—
cis-CF3
6


−113.9
d, d, m
1J(PF) = 730
PF
2




2J(FH) = 63


−119.2
d, m
2J(PFtrans) = 105
trans-CF2
2


−125.7
d, m
2J(PFcis) = 93
cis-CF2
4
















TABLE 13.3







1H-NMR data of [(CH3)2NCH2P(CH3)3][P(C2F5)3F2H] in CH2Cl2











δ, ppm
Multiplicity
J/Hz
Assignment
Integral





1.8
d
2J(PH) = 14
[(CH3)2NCH2P(CH3)3]+
9


2.4
s
—
[(CH3)2NCH2P(CH3)3]+
6


3.3
d
2J(PH) = 5
[(CH3)2NCH2P(CH3)3]+
2
















TABLE 13.4







13C{1H}-NMR data of [(CH3)2NCH2P(CH3)3][P(C2F5)3F2H] in


CH2Cl2










δ, ppm
Multiplicity
J/Hz
Assignment













6.5
d
1J(PC) = 54
[(CH3)2NCH2P(CH3)3]+


47.6
d
3J(PC) = 7
[(CH3)2NCH2P(CH3)3]+


51.6
s (br)
—
N(CH3)3


52.9
d
1J(PC) = 7
[(CH3)2NCH2P(CH3)3]+

## Claims

1. A process for the preparation of a compound of formula (1)


[Kt]x+[(CnF2n+1)ZPF5-zH]−x,  (1)


in which [Kt]x+ is an inorganic or organic cation, n is 1-8, x is 1-4, and z is 1-4, said process comprising:
in a first step, reacting a compound of formula (2)


(CnF2n+1)zPF5-z  (2)


with a hydride ion donor, and
if [Kt]x+ in formula (1) is an organic cation, in a second step, optionally reacting the product from said first step with a compound of formula (3)


[Kt]x+[X]−x,  (3),




in which [Kt]x+ stands for an organic cation and [X]− stands for a hydrophilic anion.

2. The process according to claim 1, wherein said hydride ion donor is selected from metal hydrides, borohydrides, hydridoborates, hydridoaluminates and tertiary and secondary amines.

3. The process according to claim 2, wherein said hydride ion donor is LiAlH4.

4. The process according to claim 2, wherein said hydride ion donor is a tertiary or secondary amine of formula (11)


R142N—CH2R15  (11),


where
R14 and R15 on each occurrence, independently of one another, denotes
H, where a maximum of one substituent R14 can be H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,

where R15 may also be Cl or F,
where R15 may be fully substituted by fluorine and/or one or more R14 and/or R15 may be partially substituted by halogens or partially substituted by —OR1*, —NR1*2, —CN, —C(O)NR1*2 or —SO2NR1*2,

and where one or two non-adjacent carbon atoms which are not in the α-position of the radicals R14 and/or R15 are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —SO2—, —N+R1*2—, —C(O)NR1*—, —SO2NR1*— and —P(O)R1*—; and
R1* is a non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl.

5. The process according to claim 1, wherein z stands for 2 or 3.

6. The process according to claim 1, wherein [Kt]x+ is a metal cation.

7. The process according to claim 1, wherein [Kt]x+ is an organic cation.

8. The process according to claim 7, wherein the cation [Kt]x+ is selected from ammonium, phosphonium, uronium, thiouronium, sulfonium, oxonium, guanidinium cations, heterocyclic cations and iminium cations,
where ammonium cations are given by formula (4)


[NR4]+  (4),


where
R in each case, independently of one another, denotes
H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,


where one R may be fully substituted by fluorine and/or one or more R may be partially substituted by halogens or partially substituted by —OR1, —NR1*2, —CN, —C(O)NR12 or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of the radical R are each optionally replaced by atoms and/or atom groups selected —O—, S, S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1— and —P(O)R1—;
where phosphonium cations are given by formula (5)


[PR24]+  (5),


where
R2 in each case, independently of one another, denotes
H where all substituents R2 cannot simultaneously be H, NR12,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,

where one R2 may be fully substituted by fluorine and/or one or more R2 may be partially substituted by halogens, or partially substituted by —OR1, —CN, —C(O)NR12, or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of the R2 are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, and —P(O)R1—;
where uronium cations are given by formula (6)


[C(NR3R4)(OR5)(NR6R7)]+  (6)


and thiouronium cations are given by formula (7)


[C(NR3R4)(SR5)(NR6R7)]+  (7),


where
R3 to R7 each, independently of one another, denote
H, NR1*2,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms,
which may be substituted by alkyl groups having 1-6 C atoms,



where one or more of the substituents R3 to R7 may be partially substituted by halogens, or by —OH, —OR1, —CN, —C(O)NR12, or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of R3 to R7 are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, and —P(O)R1—;
where sulfonium cations are given by formula (12))


[(Ro3S]+  (12),


where
Rostands for
NR′′′2,
straight-chain or branched alkyl having 1-8 C atoms,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
where one or more of the substituents R0 may be partially substituted by halogens, or by —OR′′′, —CN or —N(R′′′)2;
where oxonium cations are given by formula (13)


[(Ro*)3O]+  (13),


where
Ro* stands for
straight-chain or branched alkyl having 1-8 C atoms,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,

where one or more of the substituents R0* may be partially substituted by halogens, or by —OR′′′, —CN or —N(R′′′)2;
where guanidinium cations are given by formula (8)


[C(NR8R9)(NR10R11)(NR12R13)]+  (8),


where
R8 to R13 each, independently of one another, denote
H, NR1*2,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,


where one or more of the substituents R8 to R13 may be partially substituted by halogens or by —OR1, —CN, —C(O)NR12, or —SO2NR12,
and where one or two non-adjacent carbon atoms which are not in the α-position of R8 to R13 are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, and —P(O)R1—;
where heterocyclic cations are given by formula (9)


[HetN]+  (9),


where [HetN]+ is a heterocyclic cation selected from










where the substituents R1′ to R4′ each, independently of one another, denote
H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,
saturated, partially or fully unsaturated heteroaryl, heteroaryl-C1-C6-alkyl or aryl-C1-C6-alkyl,


where the substituents R1′, R2′, R3′ and/or R4′ together may form a ring system, where one or more substituents R1′ to R4′ may be partially or fully substituted by halogens or partially substituted by —OR1, —CN, —C(O)NR12, or —SO2NR12, but where R1′ and R4′ cannot simultaneously be fully substituted by halogens, and where one or two non-adjacent carbon atoms which are not bonded to the heteroatom of the substituents R1′ to R4′are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —SO2—, —N+R12—, —C(O)NR1—, —SO2NR1—, and —P(O)R1—; and
where iminium cations are given by formula (10)


[R142N═CHR15]+  (10),


where
R14 and R15 on each occurrence, independently of one another, denotes
H, where a maximum of one substituent R14 can be H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms,


where R15 may also stand for Cl or F,
where R15 may be fully substituted by fluorine and/or one or more R14 and/or R15 may be partially substituted by halogens or partially substituted by —OR1*, —NR1*2, —CN, —C(O)NR1*2 or —SO2NR1*2,
and where one or two non-adjacent carbon atoms which are not in the α-position of the radical R14 and/or R15 are each optionally replaced by atoms and/or atom groups selected from —O—, —S—, —S(O)—, —N+R1*2—, —C(O)NR1*—, —SO2NR1*— and —P(O)R1*—;
in which
R1 stands for H, non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl,
R1* stands for non- or partially fluorinated C1- to C6-alkyl, C3- to C7-cycloalkyl, unsubstituted or substituted phenyl, and
R′′′ stands for a straight-chain or branched C1-C8-alkyl.

9. The process according to claim 1, wherein the reaction in the first step is carried out at −80 to 50° C.

10. A process comprising reacting a compound of formula (1)


[Kt]x+[(cnF2n+1)zPF5-zH]−x  (1)

in which [Kt]x+ is an inorganic cation, n is 1-8, x is 1-4, and z is 1-4,
with a compound of formula (3)


[Kt]x+[X]−x  (3),



in which [Kt]x+ is an organic cation and [X]− stands for a hydrophilic anion.

11. An electrolyte composition comprising a compound of formula (1)


[Kt]x+[(CnF2n+1)zPF5-zH]−x  (1)

in which [Kt]x+is an organic cation, n is 1-8, x is 1-4, and z is 1-4.

12. A compound of formula (1)


[Kt]x+[(CnF2n+1)zPF5-zH]−x  (1)


in which [Kt]x+ is an inorganic or organic cation,
n is 1-8,
x is 1-4, and
z is 1-4,

where the compounds [(CF3)2PF3H]−K+, [(CF3)2PF3H]−[(CH3)2NH2]+, [(CF3)PF4H]−K+ and [(CF3)PF4H]−[(CH3)2NH2]+are excluded.

13. A compound according to claim 12, wherein [Kt]x+ is a metal cation.

14. A compound according to claim 12, wherein [Kt]x+ is an organic cation.

15. A process comprising:
converting a compound according to claim 1, in which [Kt]x+ stands for an organic cation, into a compound containing a [(CnF2n+1)2P(O)O]− or [(CnF2n+1)P(O)O2]−2 anion by hydrolysis.

16. The process according to claim 1, wherein the product from said first step is reacted with a compound of formula (3) to obtain a compound of formula (1) in which [Kt]x+ stands for an organic cation.

17. The process according to claim 1, wherein said hydride ion donor is a metal hydride and the product from said first step is reacted with a compound of formula (3) to obtain a compound of formula (1) in which [Kt]x+ stands for an organic cation.

18. The process according to claim 1, wherein n stands for 2, 3 or 4.

19. The process according to claim 5, wherein n stands for 2, 3 or 4.

20. The process according to claim 1, wherein compound of formula (2) is (C2F5)3PF2.

21. The process according to claim 1, wherein [Kt]x+ is an inorganic cation which is a metal cation selected from lithium, sodium, and potassium cations.

22. The process according to claim 1, wherein [Kt]x+ is an organic cation selected from propyl(dimethyl)ethylammonium, methoxyethyl(dimethyl)ethylammonium, 1-butyl-1-methylpyrrolidinium, 1-propyl-1-methylpyrrolidinium, 1-methoxyethyl-1-methylpyrrolidinium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium and 1-methyl-3-propylimidazolium.

23. The process according to claim 1, wherein [Kt]x+ is an organic cation selected from 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium.

24. The process according to claim 16, wherein [X]− is an anion selected from Cl−, Br−, I−, sulfate, sulfonate, acetate and BF4−.

25. The process according to claim 1, wherein the reaction in the first step is carried out at a temperature of −80 to 50° C. in the presence of an aprotic solvent.

26. The process according to claim 25, wherein said aprotic solvent is dioxane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, hexane, cyclohexane, benzene, dichloromethane or dichloroethane.

27. The process according to claim 16, wherein the reaction in the second step is carried out at room temperature in the presence of water or in a mixture of water and organic solvent.