# Patent

## Title
Fluoroalkylfluorophosphorane adducts

## Abstract

The invention relates to fluoroalkylfluorophosphorane adducts and the use thereof for masking OH groups in organic compounds.

## Background
The invention relates to perfluoroalkylfluorophosphorane adducts and the use thereof for masking OH groups in organic compounds.
Fluoroalkylfluorophosphoranes, in particular perfluoroalkylfluorophosphoranes, are strong Lewis acids which react very well with nucleophiles. WO 2008/092489 discloses, for example, the reaction of 1-ethyl-3-methylimidazolium chloride with tris(pentafluoroethyl)difluorophosphorane in acetonitrile, where the ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)difluorochlorophosphate is formed.
However, the reaction of fluoroalkylfluorophosphoranes, in particular perfluoroalkylfluorophosphoranes, with oxygen-containing nucleophiles generally results in complex mixtures of compounds.
However, there continues to be a need in the area of the synthesis of chemical compounds to use fluoroalkylfluorophosphoranes, in particular perfluoroalkylfluorophosphoranes, as starting material also for the reaction with oxygen-containing nucleophiles.
Surprisingly, it has been found that the reactivity and thus the Lewis acidity of fluoroalkylfluorophosphoranes, in particular perfluoroalkylphosphoranes, can be controlled in a targeted manner by preparing adducts with suitable Lewis bases. These adducts are excellent starting materials for the reaction with oxygen-containing nucleophiles, and defined compounds and not complex mixtures are formed in the reaction.
The invention accordingly relates firstly to the compounds of the formula I

[P(Rf)nF5-nD]−  I,

where Rf in each case, independently of one another, denotes a straight-chain or branched fluoroalkyl group having 1 to 8 C atoms,
n denotes 1, 2 or 3 and
D denotes a Lewis base which contains at least one N atom, O atom or at least one P atom and the at least one N, O or P atom has a free electron pair or which contains at least one N—C(═O) group which coordinates to the P atom via the oxygen, and/or tautomers or stereoisomers, including mixtures thereof in all ratios.
A straight-chain or branched fluoroalkyl group having 1 to 8 C atoms is a partially fluorinated or perfluorinated straight-chain or branched alkyl group having 1 to 8 C atoms, i.e. in the case of a perfluorinated alkyl group all H atoms of this alkyl group have been replaced by F. In the case of a partially fluorinated alkyl group having 1 to 8 C atoms, the alkyl group has at least one F atom, 1, 2, 3 or 4 H atoms are present and the other H atoms of this alkyl group have been replaced by F. Known straight-chain or branched alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl. Preferred examples of the partially fluorinated straight-chain or branched alkyl group Rf are CF3—CHF—CF2—, CF2H—CF2—, CF3—CF2—CH2—, CF3—CF2—CH2—CH2— or CF3—CF2—CF2—CF2—CF2—CF2—CH2—CH2—.
A straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms is, for example, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, n-nonafluorobutyl, sec-nonafluorobutyl, tert-nonafluoro-butyl, dodecafluoropentyl, 1-, 2- or 3-trifluoromethyloctafluorobutyl, 1,1-, 1,2- or 2,2-bis(trifluoromethyl)pentafluoropropyl, 1-pentafluoroethylhexafluoropropyl, n-tridecafluorohexyl, n-pentadecafluoroheptyl or n-heptadecafluorooctyl. Preferred examples of the perfluorinated alkyl group Rf are pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, nonafluorobutyl, sec-nonafluorobutyl or tert-nonafluorobutyl.
The substituents Rf in the compounds of the formula I are preferably, in each case independently of one another, straight-chain or branched perfluoroalkyl groups having 1 to 8 C atoms, particularly preferably, in each case independently of one another, perfluoroalkyl groups having 1 to 4 C atoms, very particularly preferably, in each case independently of one another, perfluoroalkyl groups having 2 to 4 C atoms, especially very particularly preferably pentafluoroethyl or nonafluorobutyl. The substituents Rf in the compounds of the formula I are preferably identical.
The number n denotes 1, 2 or 3. n preferably stands for the number 2 or 3, very particularly preferably for the number 3.
Preferred Lewis bases D which have the desired properties are selected, for example, from the group aromatic amine, which has basic properties, dialkyl ether, aromatic or aliphatic tertiary phosphine, dialkylformamide, dialkylacetamide or N-alkyl-2-pyrrolidone, where the said alkyl groups have, in each case independently of one another, 1 to 8 C atoms.
A straight-chain or branched alkyl group having 1 to 8 C atoms is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl or n-octyl.
Preferred aromatic amines are, for example, pyridine, morpholine, piperazine, imidazole, oxazole or thiazole, each of which may be substituted by alkyl groups having 1 to 8 C atoms or dialkylamino groups, which each have, independently of one another, 1 to 8 C atoms. The aromatic amine is particularly preferably selected from the group pyridine, 4-methylpyridine or 4-dimethylaminopyridine.
A preferred dialkyl ether is diethyl ether.
Triphenylphosphine oxide (phenyl3P═O) or trimethyl phosphate (methyl3PO4) can also be employed as Lewis base D.
Preferred aromatic or aliphatic tertiary phosphines are, for example, triphenylphosphine, diphenylmethylphosphine, trimethylphosphine, triethylphosphine, tri-i-propylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine. A particularly preferred tertiary aliphatic phosphine is trimethylphosphine.
Preferred dialkylformamides are, for example, dimethylformamide, diethylformamide, dipropylformamide. A particularly preferred dialkylformamide is dimethylformamide.
Preferred dialkylacetamides are, for example, dimethylacetamide, diethylacetamide or dipropylacetamide.
Preferred N-alkyl-2-pyrrolidones are, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone or N-butyl-2-pyrrolidone.
Particularly preferred Lewis bases D are selected, for example, from the group aromatic amine or dialkylformamide, as described above.
Very particularly preferred Lewis bases are 4-dimethylaminopyridine or dimethylformamide. An especially very particularly preferred Lewis base is 4-dimethylaminopyridine.
The invention is furthermore directed to a process for the preparation of the compounds of the formula I, as described above or as preferably described, characterised in that a fluoroalkylfluorophosphorane of the formula II

(Rf)nPF5-n  II,

where Rf in each case, independently of one another, denotes a straight-chain or branched fluoroalkyl group having 1 to 8 C atoms and n denotes 1, 2 or 3, is reacted with a Lewis base D, where the Lewis base contains at least one N atom, O atom or at least one P atom and the at least one N, O or P atom has a free electron pair, or contains at least one N—C(═O) group which coordinates to the P atom via the oxygen.
For the preferred meanings of the substituents Rf, the number n and the Lewis base D, the comments as described above apply.
The preparation of perfluoroalkylfluorophosphoranes of the formula II can be carried out 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].
Fluoroalkylfluorophosphoranes can be obtained by free-radical addition of dialkyl phosphites, (RO)2P(O)H or phosphines onto fluoroolefins [N. O. Brace, J. Org. Chem., 26 (1961), p. 3197-3201; P. Cooper, R. Fields, R. N. Haszeldine, J. Chem. Soc., Perkin I, 1975, p. 702-707; G. M. Burch, H. Goldwhite, R. N. Haszeldine, J. Chem. Soc., 1963, p. 1083-1091] or to fluoro-alkylolefins see P. Kirsch, Modern Fluoroorganic Chemistry, WILEY-VCH, 2004, p. 174], following a chlorination/fluorination or an oxidative fluorination. The reaction of the phosphorane of the formula II with the Lewis base, as described above or as preferably described, is carried out at temperatures of 0 to 80° C., preferably 15 to 30° C., in the presence of an organic solvent and in a water-free atmosphere.
Suitable solvents here are acetonitrile, dioxane, dichloromethane, dimethoxyethane, dimethyl sulfoxide, tetrahydrofuran or dialkyl ethers, for example diethyl ether or methyl t-butyl ether.
The Lewis base D is preferably employed in excess, i.e. the added molar amount of Lewis base is greater than the molar amount of starting compound of the formula II, as described above.
The fluoroalkylfluorophosphorane adducts of the formula I, in particular the perfluoroalkylfluorophosphorane adducts of the formula I, can be isolated. However, they can also be reacted with nucleophiles in the reaction mixture of the preparation process.
The structure of the compounds of the formula I can be interpreted by way of example as follows, which describes the stereoisomeric variability of the position of the F and fluoroalkyl groups on the P. Base here denotes the Lewis base D.




In particular, the compounds of the formula I, as described above or as preferably described, can be reacted with nucleophiles which contain an oxygen atom.
The reaction of the compounds of the formula I, as described above, with water (HOH), an alcohol (ROH) or a carboxylic acid (RCOOH), for example, results in the preparation of defined compounds having a corresponding phosphate anion [P(Rf)nF5-nX]−, where the proton liberated is scavenged and stabilised by the Lewis base, and X denotes OH, OR or OC(O)R, i.e. denotes the radical of the alcohol employed or of the carboxylic acid, and Rf and the number n have a meaning indicated above. Examples of such reactions are indicated in the example part.
However, the compounds of the formula I are also eminently suitable for masking OH groups of an organic compound.
The invention is therefore furthermore directed to a method for masking at least one OH group of an organic compound, characterised in that this compound is reacted with a compound of the formula I, as described above or as preferably described.
The choice of the organic compound is unrestricted, so long as the compound carries at least one OH group which is able to react with the compound of the formula I.
The organic compound containing at least one OH group is preferably an aliphatic or aromatic alcohol containing at least one OH group or an oligomeric or polymeric compound containing at least one OH group.
Suitable aliphatic or aromatic alcohols containing at least one OH group are methanol, ethanol, butanol, hexanol, octanol, allyl alcohol, phenol, hydroquinone, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,2,3-propanetriol (glycerol), oxo compounds, such as, for example, glycerol aldehyde, or further polyols, i.e. compounds containing more than 3 OH groups.
The term polyols is applied to a group of organic compounds which contain a plurality of hydroxyl groups, here at least three OH groups. Polyols may have either a linear or cyclic structure.
From the group of the aliphatic or aromatic alcohols, so-called polyols are particularly preferred.
The polyols include, for example, D-threitol, L-threitol, erythrol, D-arabinitol, L-arabinitol, adonitol, xylitol, D-sorbitol, D-mannitol or galactitol. Furthermore, the term polyols also encompasses the group of the carbohydrates, including monosaccharides, disaccharides, oligosaccharides and polysaccharides or polyhydroxy acids thereof.
Monosaccharides are, for example, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, dihydroxyacetone, erythrulose, ribulose, xylulose, psicose, fructose, sorbose, tagatose, including all stereoisomeric forms, in particular the D and L forms, and alpha- or beta-anomers.
Disaccharides are, for example, sucrose, lactose, trehalose, maltose or cellobiose.
Oligosaccharides are carbohydrates consisting of at least three carbohydrate units, for example raffinose or acarbose.
Polysaccharides are characterised in that they are composed of many carbohydrate units which form a macromolecule. Starch, glycogen or cellulose are, for example, polysaccharides.
The polyols also include polyester-polyols or polyether-polyols.
The organic compound containing at least one OH group is preferably a polyol or a polyethylene glycol.
Polyols can be described by the sub-formula [—CH2CHOH—]n, having molecular weights between 5000 and 200,000, for example in polyvinyl alcohol, or as copolymer with other polymers, for example as poly-(vinyl alcohol-co-ethylene) [(CH2CH2)x[CH2CHOH]y having molecular weights between 5000 and 200,000.
Polyethylene glycol is liquid or solid, depending on the chain length, and can be described by the formula H[—O—(CH2)2—O]m—H. Polyethylene glycols up to a chain length m of 600 monomer units are liquid. Solid from a chain length of 600 monomer units.
Polyols are particularly preferably masked. In the case of polyols, the masking of the OH groups can take place completely or partially, depending on the amount of compounds of the formula I employed, as described above or as preferably described. Through specific control of the amount of compounds of the formula I employed, a corresponding proportion of OH groups in the polyol can be specifically masked. The remaining OH groups are furthermore accessible to further derivatisation.
The following working examples are intended to explain the invention without limiting it. The invention can be carried out correspondingly throughout the 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
The substances obtained are characterised by means of mass spectrometry, elemental analysis and NMR spectroscopy. NMR spectra are recorded using the Avance III 300 spectrometers, from Bruker, Karlsruhe. Acetone-d6 is used in a capillary as lock substance. The referencing is carried out using external reference: TMS for 1H and 13C spectra; CCl3F— for 19F and 80% H3PO4— for 31P spectra.
Example 1
Preparation of [P(C2F5)3F2(dmap)]




2.8 g (22.9 mmol) of 4-(dimethylamino)pyridine are initially introduced in 100 ml of diethyl ether, and 12.2 g (28.6 mmol) of (C2F5)3PF2 are slowly added. After stirring for 15 minutes, volatile constituents are removed in vacuo, leaving a colourless solid.
Yield (based on DMAP): 12.1 g (97%). Melting point: 150-153° C.
31P, δ, ppm=−144.5, t, quin, t, 1J(PF)=986 Hz, 2J(PFcis)=107 Hz,
2J(PFtrans)=97 Hz, assignment [P(C2F5)3F2(dmap)] in diethyl ether.
19F, δ, ppm=−80.4 m (trans-CF3); −81.6 m (cis-CF3); −99.4 d (PF), 1J(PF)=986 Hz, −111.5 m (br) (cis-CF2), −115.3 d,m (trans-CF2), 2J(PF)=95 Hz. Measurement in CDCl3.
1H, δ, ppm=3.2 s (N(CH3)2), 6.7 d (H2), 3J(HH)=7 Hz, 8.4 m (br) (H1) Measurement in CDCl3.
13C, δ, ppm=38.6a s (—N(CH3)2), 105.9a s (C1), 116.7b m (—CF2CF3), 118.2b m (—CF2CF3), 138.9a m (C2), 156.1 a s (C3). Measurement in CDCl3.
1{1H}b{19F}
Elemental analysis data of [P(C2F5)3F2(dmap)]















N
C
H





















calculated
5.11
28.48
1.84



experimental
4.91
28.63
1.67










Example 2
Preparation of [PPh4][P(C2F5)3F2OH]




0.96 g (1.75 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in ether, and excess water is added. After stirring for 30 minutes, 0.66 g (1.75 mmol) of [PPh4]Cl, dissolved in 2 ml of water, are added, and the mixture is again stirred for 20 minutes. The aqueous phase is subsequently separated off, and the organic phase is extracted three times with water. The organic phase is dried in vacuo, leaving a colourless solid as residue. Yield (based on [P(C2F5)3F2(dmap)]: 1.29 g (94%). Melting point: 139° C.
31P-NMR spectroscopic data of [PPh4][P(C2F5)3F2OH] in CD3CN
31P, δ, ppm=23.2 s ([PPh4][P(C2F5)3F2OH]), −148.3 t, sept ([PPh4][P(C2F5)3F2OH]), 1J(PF)=845 Hz, 2J(PF)=86 Hz.
19F (CD3CN), δ, ppm=−80.1 m (trans-CF3); −81.2 m (cis-CF3); −86.6 d, m (PF), 1J(PF)=846 Hz, −114.1 d(cis,trans-CF2), 2J(PF)=86 Hz.
1H (CD3CN), δ, ppm=5.1 t, d ([P(C2F5)3F2OH]), 3J(FH)=14 Hz, 2J(PH)=3 Hz, 7.8-8.1 m ([PPh4]+).
13C (CD3CN), δ, ppm=118.5a d (C1), 1J(PC)=90 Hz, 119.1 b m (—CF2CF3), 120.7b m (—CF2CF3), 130.3a d (C2), 2J(PC)=13 Hz, 134.7a d (C3), 3J(PC)=10 Hz, 135.4a d (C4), 4J(PC)=3 Hz.
a{1H}b{19F}
Elemental analysis data of [PPh4][P(C2F5)3F2OH]














C
H




















calculated
46.05
2.71



experimental
46.40
2.79










Example 3
Preparation of [HDMAP][(C2F5)3PF2OC(O)CH3]




0.52 g (0.96 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in dichloromethane. 0.19 g (3.17 mmol) of acetic acid are added at room temperature, and the reaction mixture is stirred for 3 hours. Volatile constituents are subsequently removed in vacuo, leaving a colourless solid. Yield (based on [P(C2F5)3F2(dmap)]): 0.54 g (93%)
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC(O)CH3] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







−146.3
t, quin, t
1J(PF) = 915
[P(C2F5)3F2OC(O)CH3]−




2J(PFcis) = 103




2J(PFtrans) = 84









19F-NMR spectroscopic data of [HDMAP][(C2F5)3PF2OC(O)CH3] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−80.2
m
—
trans-CF3
1


−81.8
m
—
cis-CF3
2


−86.9
d, m
1J(PF) = 923
PF
0.6


−115.3
d, m
2J(PF) = 85
trans-CF2
—


−116.0
d, m
2J(PF) = 103
cis-CF2
—









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC(O)CH3] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















1.9
s
—
—OC(O)CH3
1.6


3.2
s
—
—N(CH3)2
3


6.9
d
3J(HH) = 7
H1
1


7.9
d
3J(HH) = 7
H2
1









13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC(O)CH3] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







 23.3 a
s
—
—OC(O)CH3


 39.6 a
s
—
—N(CH3)2


107.1 a
s
—
C1


116.7 b
m
—
—CF2CF3


120.0 b
m
—
—CF2CF3


138.6 a
s
—
C2


157.7 a
s
—
C3


166.3 a
d
2J(PC) = 18
—OC(O)CH3





a {1H}


b {19F}






Example 4
Preparation of [HDMAP][P(C2F5)3F2OPh]




0.52 g (0.95 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in diethyl ether. 0.13 g (1.34 mmol) of phenol are added at room temperature, and the reaction mixture is stirred for 12 hours. Two phases form. The solvent is removed in vacuo, leaving a clear, colourless liquid.
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







−147.5
t, quin, t
1J(PF) = 893
[P(C2F5)3F2OPh]−




2J(PFcis) = 98




2J(PFtrans) = 84









19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−79.4
m
—
trans-CF3
—


−80.5
m
—
cis-CFs
—


−85.5
d, m
1J(PF) = 896
PF
—


−111.5
d, m
2J(PF) = 97
cis-CF2
—


−112.7
d, m
2J(PF) = 79
trans-CF2
—









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















3.4
s
—
—N(CH3)2
3


6.7
d
3J(HH) = 7
H1
1


7.1
m
—
—OC6H5
2.2


8.3
d
3J(HH) = 7
H2
1









13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







 39.7 a
s
—
—N(CH3)2


106.9 a
s
—
C1


115.2 a
s
—
C5


118.1 b
m
—
—CF2CF3


119.7 b
m
—
—CF2CF3


120.4 a
s
—
C6/7


128.9 a
s
—
C6/7


138.8 a
s
—
C2


157.0 a
s
—
C4


157.6 a
s
—
C3





a {1H}


b {19F}






Example 5
Preparation of [HDMAP]2[{P(C2F5)3F2O}2C6H4]




1.11 g (2 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in diethyl ether. 0.11 g (1 mmol) of hydroquinone are added at room temperature, and the reaction mixture is stirred for 4 hours. Volatile constituents are subsequently removed in vacuo, leaving a colourless solid. Yield (based on hydroquinone): 0.85 g (78%).
31P-NMR spectroscopic data of [HDMAP]2[{P(C2F5)3F2O}2C6H4] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







−148.0
t, quin, t
1J(PF) = 882
[{P(C2F5)3F2O}2C6H4]2−




2J(PFcis) = 96




2J(PFtrans) = 78









19F-NMR spectroscopic data of [HDMAP]2[{P(C2F5)3F2O}2C6H4] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−80.4
m
—
trans-CF3
1


−81.6
m
—
cis-CF3
2


−86.9
d, m
1J(PF) = 881
PF
0.6


−112.9
d, m
2J(PF) = 98
cis-CF2
1.3


−113.9
d, m
2J(PF) = 80
trans-CF2
0.7









1H-NMR spectroscopic data of [HDMAP]2[{P(C2F5)3F2O}2C6H4] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















3.1
s
—
—N(CH3)2
3


6.8
m
—
H5/6
0.5


6.8
d
3J(HH) = 8
H1
1


7.9
d
3J(HH) = 8
H2
1









Elemental analysis data of [HDMAP]2[{P(C2F5)3F2O}2C6H4]















N
C
H





















calculated
4.67
32.07
1.51



experimental
4.73
32.40
2.26










Example 6
Preparation of [HDMAP][P(C2F5)3F2OEt]




10.6 g (230 mmol) of ethanol are initially introduced in 100 ml of Et2O. 12.5 g (23 mmol) of [P(C2F5)3F2(dmap)] are added at room temperature, and the mixture is stirred for 30 minutes. Volatile substances are subsequently removed overnight in vacuo, leaving a colourless solid. Yield (based on [P(C2F5)3F2(dmap)]): 13.6 g (100%). Melting point: 75-78° C.
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







−149.4
t, sept
1J(PF) = 869
[P(C2F5)3F2OC2H5]−




2J(PF) = 88









19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−80.6
m
—
trans-CF3
1


−81.8
m
—
cis-CF3
2


−94.5
d
1J(PF) = 869
PF
0.6


−113.5
d, m
2J(PF) = 83
trans-CF2
0.6


−114.4
d, m
2J(PF) = 86
cis-CF2
1.3









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















1.1
t, d
3J(HH) = 7
—OCH2CH3
1.4




4J(PH) = 1


3.2
s
—
—N(CH3)2
3


4.0
pseudo-
3J(PH) = 7
—OCH2CH3
0.9



quin
3J(HH) = 7


5.3
s
—
—NH+
1


6.8
d
3J(HH) = 7
H1
1


8.0
d
3J(HH) = 7
H2
1









13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







 16.0 a
d
3J(CP) = 10
—OCH2CH3


 39.6 a
s
—
(CH3)2N—


 61.8 a
m
—
—OCH2CH3


107.1 a
s
—
C1


118.8 b
m
—
—CF2CF3


122.5 b
m
—
—CF2CF3


138.5 a
s
—
C2


157.9 a
s
—
C3





a {1H}


b {19F}






Elemental analysis data of [HDMAP][P(C2F5)3F2OEt]















N
C
H





















calculated
4.71
30.32
2.71



experimental
4.74
30.32
2.69










Example 7
Preparation of [HDMAP][P(C2F5)3F2OCH2CF3]




2.5 g (4.5 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in diethyl ether. 0.9 g (9.0 mmol) of trifluoroethanol are added at room temperature, and the reaction mixture is stirred for 12 hours. Volatile constituents are subsequently removed in vacuo, leaving a colourless solid. Yield (based on [P(C2F5)3F2(dmap)]): 2.8 g (95%). Melting point: 91-93° C.
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







−149.9
t, sept
1J(PF) = 886
[P(C2F5)3F2OCH2CF3]−




2J(PF) = 88









19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−75.4
s
—
[P(C2F5)3F2OCH2CF3]−
1


−79.6
m
—
trans-CF3
1


−80.8
m
—
cis-CF3
2


−93.8
d, m
1J(PF) = 883
PF
0.5


−112.2
d, m
—
trans-, cis-CF3
2.2









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral







3.2
s
—
—N(CH3)2
3


4.4
quar, d
3J(FH) = 9
—OCH2CF3
1




3J(PH) = 4


6.8
d
3J(HH) = 7
H1
1


8.0
d
—
H2
1









13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN













δ, ppm
Multiplicity
J[Hz]
Assignment







 39.6 a
s
—
—N(CH3)2


 64.1 a
m
—
—OCH2CF3


106.9 a
s
—
C1


118.8 b
m
—
—CF2CF3


120.4 b
m
—
—CF2CF3


124.5 b
m
—
—OCH2CF3


138.9 a
s
—
C2


157.7 a
s
—
C3





a {1H}


b {19F}






Elemental analysis data of [HDMAP][P(C2F5)3F2OCH2CF3]















N
C
H





















calculated
4.32
27.79
2.02



experimental
4.47
28.10
1.64










Example 8
Preparation of [HDMAP][P(C2F5)3F2ODec]




0.69 g (1.25 mmol) of [P(C2F5)3F2(dmap)] are dissolved in Et2O. 0.20 g (1.25 mmol) of 9-decen-1-ol are added at room temperature, and the mixture is stirred for 1.5 hours. The reaction mixture is subsequently dried in vacuo, leaving a clear viscous liquid. Yield (based on [P(C2F5)3F2(dmap)]): 0.88 g (99%). Melting point: <20° C.
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3













δ, ppm
Multiplicity
J[Hz]
Assignment







−147.2
t, sept
1J(PF) = 873
[P(C2F5)3F2OC10H19]−




1J(PF) = 88









19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−79.7
m
—
trans-CF3
1


−81.0
m
—
cis-CFs
2.1


−94.9
d, m
1J(PF) = 876
PF
0.5


−113.0
d, m
—
cis-, trans-CF2
2.1









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















1.2-1.6
m
—
H6-H10
5.7


1.5
t
3J(HH) = 7
H5
—


2.0
quin
3J(HH) = 7
H11
1


3.2
s
—
—N(CH3)2
3


3.7
t
3J(HH) = 7
H4
0.6


4.9-5.0
m
—
H13
0.9


5.8
m
—
H12
0.5


6.7
d
3J(HH) = 7
H1
1


7.8
d
3J(HH) = 7
H2
1









13C{1H}-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3













δ, ppm
Multiplicity
J[Hz]
Assignment







25.7; 28.9;
s
—
C6-C10


29.0; 29.3;


29.4


32.8
s
—
C5


33.8
s
—
C11


40.0
s
—
—N(CH3)2


63.2
s
—
C4


107.0
s
—
C1


114.1
s
—
C13


138.5
s
—
C2


139.3
s
—
C12


157.4
s
—
C3









Example 9
Preparation of [HDMAP][P(C2F5)3F2OC2H4OH]




0.60 g (1.1 mmol) of [P(C2F5)3F2(dmap)] are initially introduced in diethyl ether. 0.10 g (1.6 mmol) of ethylene glycol are added at room temperature, and the reaction mixture is stirred for 24 hours. Volatile constituents are subsequently removed in vacuo, leaving a colourless solid. Yield (based on [P(C2F5)3F2(dmap)]): 0.61 g (89%). Melting point: 88° C. (softening of the sample), 91° C. decomposition.
31P-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC2H4OH]













δ, ppm
Multiplicity
J[Hz]
Assignment







−149.2
t, sept
1J(PF) = 871
[P(C2F5)3F2OC2H4OH]−




2J(PF) = 86









19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC2H4OH]














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−79.3
m
—
trans-CF3
1


−80.4
m
—
cis-CFs
1.8


−93.2
d, m
1J(PF) = 873
PF
0.3


−112.6
d, m
2J(PF) = 83
trans-, cis-CF2
1.8









1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC2H4OH]














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















3.2
s
—
—N(CH3)2
3


3.5
t
3J(HH) = 4
H5
0.8


4.0
pseudo-quar
3J(HH) = 4
H4
0.6




3J(PH) = 4


6.8
d
3J(HH) = 8
H1
1


8.0
d
3J(HH) = 8
H2
1









13C-NMR spectroscopic data of [H DMAP][P(C2F5)3F2OC2H4OH]













δ, ppm
Multiplicity
J[Hz]
Assignment







 39.6 a
s
—
—N(CH3)2


 62.1 a
d
2J(PC) = 9
C4


 67.8 a
s
—
C5


106.8 a
s
—
C1


116.7 b
m
—
—CF2CF3


120.6 b
m
—
—CF2CF3


138.6 a
s
—
C2


157.6 a
s
—
C3





a {1H}


b {19F}






Elemental analysis data of [HDMAP][P(C2F5)3F2OC2H4OH]















N
C
H





















calculated
4.59
29.52
2.64



experimental
4.62
29.54
2.28










Example 10
Preparation of [P(C2F5)3F2(dmf)]




0.12 g (1.7 mmol) of DMF are initially introduced in about 15 ml of diethyl ether, and 1.02 g (2.4 mmol) of (C2F5)3PF2 are added. The reaction mixture is stirred at room temperature for 45 minutes. The solvent and excess (C2F5)3PF2 are subsequently removed in vacuo, leaving a colourless solid. Yield (based on DMF): 0.84 g (99%).
31P-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−142.1
t, t, quin
2J(PF) = 960
[P(C2F5)3F2(dmf)]




J(PFtrans) = 87




2J(PFcis) = 103









19F-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−81.4
m
—
trans-CF3
1


−82.4
m
—
cis-CF3
2


−92.6
d, m (br)
1J(PF) = 947
PF
0.3


−113.8
m (br)
—
cis-CF2
1


−116.4
d
2J(PF) = 88
trans-CF2
0.6









1H-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















2.7
s
—
CH3 (a)
1


3.1
s
—
CH3 (b)
0.9


8.4
s
—
[P(C2F5)3F2(OCHNMe2)]
0.3









13C-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







 34.6 a
(hidden)
—
CH3 (a)


 39.8 a
quar
1J(CH) = 143
CH3 (b)


117.0 b
d, m
1J(CP) = 249
—CF2CF3


119.0 b
d, m
2J(CP) = 30
—CF2CF3


163.2 a
d
1J(CH) = 218
[P(C2F5)3F2(OCHNMe2)]





a {1H}


b {19F}






Example 11
Reaction of [P(C2F5)3F2(dmf)] with H2O




A few drops of water are added to [P(C2F5)3F2(dmf)] in DMF. The reaction solution is investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OH] in Aceton-d6













δ, ppm
Multiplicity
J[Hz]
Assignment







−147.9
t, sept
1J(PF) = 847
[H(dmf)n][P(C2F5)3F2OH]




2J(PF) = 86









19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OH] in acetone-d6














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−80.5
m
—
trans-CF3
1


−81.5
m
—
cis-CF3
1.9


−87.0
d, m
1J(PF) = 839
PF
0.6


−114.5
d
2J(PF) = 85
cis-, trans-CF2
1.9









1H-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OH] in acetone-d6














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















2.7
s
—
CH3 (a)
1.1


3.0
s
—
CH3 (b)
1


8.8
s
—
[H(OHCNMe2)n]
—









Example 12
Reaction of [P(C2F5)3F2(dmf)] with EtOH




A few drops of ethanol are added to [P(C2F5)3F2(dmf)] in DMF. The reaction solution is investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OEt] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−148.6
t, pseudo-sept
1J(PF) = 871
[H(dmf)n][P(C2F5)3F2OEt]









19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OEt] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−79.2
m
—
trans-CF3
1


−80.5
m
—
cis-CF3
1.9


−93.1
d, m
1J(PF) = 871
PF
0.6


−112.3
d, m
2J(PF) = 83
trans-CF2
—


−113.1
d, m
2J(PF) = 86
cis-CF2
—









Example 13
Reaction of (C4F9)3PF2 with DMF




(C4F9)3PF2 is added to excess DMF. The reaction solution is investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [P(C4F9)3F2(dmf)] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−135.5
t, m
1J(PF) = 999
[P(C4F9)3F2(dmf)]




2J(PF) = 102









19F-NMR spectroscopic data of [P(C4F9)3F2(dmf)] in DMF a














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral







−82.1
s
—
CF3
—


−108.1-−126.2
m
—
CF2
—









a The resonance of the fluorine atoms bonded to the phosphorus atom is covered by other resonances.
1H-NMR spectroscopic data of [P(C4F9)3F2(dmf)] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral







2.7
s
—
CH3 (a)
0.9


3.1
s
—
CH3 (b)
1


8.4
s
—
[P(C4F9)3F2(OCHNMe2)]
0.3









Example 14
Reaction of [P(C4F9)3F2(dmf)] with EtOH




A few drops of ethanol are added to [P(C4F9)3F2(dmf)] in DMF. The reaction mixture is investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [H(dmf)n][P(C4F9)3F2OEt] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−143.3
t, m
1J(PF) = 903
[H(dmf)n][P(C4F9)3F2OEt]




2J(PF) = 88









19F-NMR spectroscopic data of H[P(C4F9)3F2OEt]. nDMF in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral







−82.3
m
—
CF3
—


−92.3
d, m
1J(PF) = 899
PF
—


−109.6-−127.6
m
—
CF2
—









Example 15
Preparation of [P(C2F5)2F3(dmf)]




0.09 g (1.2 mmol) of DMF are initially introduced in about 15 ml of diethyl ether, and 1.5 mmol of (C2F5)2PF3 are condensed on. The reaction mixture is investigated by NMR spectroscopy. Two conformers, IIb and Ib, form on slow thawing. IIb is converted into Ib within a few hours at room temperature. After stirring at room temperature for 30 minutes, the solvent is removed in vacuo, leaving a colourless solid. Yield (based on DMF): 0.47 g (97%).
31P-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−146.6
d, t, quin, d
1J(PFA) = 847
[P(C2F5)2F3(dmf)] (IIb)




1J(PFB) = 922




2J(PF) = 95




3J(PH) = 7


−148.7
d, t, quin
1J(PFA) = 947
[P(C2F5)2F3(dmf)] (Ib)




1J(PFB) = 986




2J(PF) = 108









19F-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−58.7
d, m
1J(PFA) = 848
PFA (IIb)
0.3


−69.1
d, m
1J(PFA) = 948
PFA (Ib)
0.8


−74.9
d, d, m
1J(PFB) = 987
PFB (Ib)
1.7




2J(FBFA) = 45


−76.2
d, d, m
1J(PFB) = 922
PFB (IIb)
0.7




2J(FBFA) = 46


−82.7
m
—
CF3 (IIb)
1.0


−83.4
m
—
CF3 (IIb)/CF3 (Ib)
6.2


−117.5
d, m
2J(PF) = 95
CF2 (IIb)
0.6


−118.7
d, d, t, m
2J(PF) = 108
CF2 (Ib)
3.4




3J(FFA) = 10




3J(FFB) = 11


−119.5
d, m
2J(PF) = 93
CF2 (IIb)
0.6









1H-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















2.1
s
—
CH3 (a) (IIb)
0.3


2.1
s
—
CH3 (a) (Ib)
1


2.4
s
—
CH3 (b) (IIb)
0.2


2.5
s
—
CH3 (b) (Ib)
1


7.8
s
—
[P(C2F5)2F3(OCHNMe2)] (Ib)
0.3


10.5
s (br)
—
[P(C2F5)2F3(OCHNMe2)] (IIb)
—









13C-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







 35.0 a
(hidden)
—
CH3 (a) (Ib)


 40.0 a
quar
1J(CH) = 144
CH3 (b) (Ib)


115.5 b
d, m
1J(CP) = 329
−CF2CF3


119.4 b
d, m
2J(CP) = 32
−CF2CF3


163.4 a
d, t
1J(CH) = 214
[P(C2F5)2F3(OCHNMe2)] (Ib)





a {1H}


b {19F}






Example 16
Reaction of [P(C2F5)2F3(dmf)] with H2O




Water is condensed onto a solution of [P(C2F5)2F3(dmf)] (Ib) in DMF at −196° C. The reaction mixture is warmed to room temperature and investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OH] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−154.4
d, t, quin
1J(PFA) = 910
[H(dmf)n][P(C2F5)2F3OH]




1J(PFB) = 926




2J(PF) = 108









19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OH] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−63.2
d, m
1J(PF) = 910
PFA
0.6


−76.0
d, d, m
1J(PF) = 926
PFB
2




2J(FF) = 46


−83.4
d, t
3J(PF) = 11
CF3
6




3J(FF) = 7


−118.9
d, quar
2J(PF) = 103
CF2
4




3J(FF) = 10









Example 17
Reaction of [P(C2F5)2F3(dmf)] with EtOH




Ethanol is condensed onto a solution of [P(C2F5)2F3(dmf)] (Ib) in DMF at −196° C. The reaction mixture is warmed to room temperature and investigated by NMR spectroscopy.
31P-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OEt] in DMF













δ, ppm
Multiplicity
J[Hz]
Assignment







−152.6
d, t, quin
1J(PFA) = 860
[H(dmf)n][P(C2F5)2F3OEt]




1J(PFB) = 876




2J(PF) = 94









19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OEt] in DMF














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−57.2
d, m
1J(PF) = 860
PFA
1


−78.5
d, d, m
1J(PF) = 876
PFB
2.5




2J(FF) = 47


−83.5
d, t
3J(PF) = 13
CF3
8




3J(FF) = 7


−119.3
d, d, t
2J(PF) = 94
CF2
5




3J(FFA) = 16




3J(FFB) = 8









Example 18
Reaction of (C2F5)3PF2. DMAP with 2-[2-(aminoethyl)-amino]ethanol




Experimental Procedure:
6.50 g (11.86 mmol) of (C2F5)3PF2. DMAP in 80 ml of dichloromethane are initially introduced in a 100 ml Schlenk flask under protective gas, and 1.23 g (11.86 mmol) of 2-[2-(aminoethyl)amino]ethanol are added dropwise to the solution at 0° C. After the addition, the ice bath is removed, and the mixture is stirred at RT overnight. 19F- and 31P-NMR reaction checks are recorded next morning.
The reaction solution is then freed from CH2Cl2 and all volatile constituents in vacuo, leaving a slightly yellow powder.
Crude yield: 7.71 g (91.7% of theory)
If the reaction is carried out in DMF instead of in CH2Cl2, another isomer forms in which the two F atoms on the phosphorus are different.
NMR data: in CD2Cl2














Nucleus
δ (ppm)
Splitting
Coupling
Assignment



















31P
−148.9
t, sept
1JPF = 879
—PF2(C2F5)3





2JPF = 87


19F
−94.6
d
1JPF = 879
—PF2(CF2CF3)3



−81.2
m

—PF2(CF2CF3)3 (6F)



−80.0
m

—PF2(CF2CF3)3 (3F)



−113.4
m

—PF2(CF2CF3)3 (4F)



−113.7
m

—PF2(CF2CF3)3 (2F)


1H
8.02
d
3JHH = 7.0
DMAP (2H)



6.67
d
3JHH = 7.0
DMAP (2H)



5.61
s, br

4H



4.19
m

2H



3.13
s

DMAP (6H)



2.89
m

6H


13C
155.9
s

DMAP



144.1
s

DMAP



106.8
s

DMAP



63.2
m

—O—CH2—



48.9
d
3JCP = 8.7
—O—CH2—CH2—N—



48.1
s

H2N—(CH2)2—N—



39.2
s

DMAP



38.2
s

H2N—(CH2)2—N—









Example 19
Reaction of (C2F5)3PF2. DMAP with ethyl 6-hydroxyhexanoate




Experimental Procedure:
3.30 g (6.02 mmol) of (C2F5)3PF2. DMAP in 40 ml of dichloromethane are initially introduced in a 100 ml Schlenk flask under protective gas, and 0.96 g (6.02 mmol) of ethyl 6-hydroxyhexanoate is added dropwise to the solution at 0° C. After the addition, the ice bath is removed, and the mixture is stirred at RT overnight. 19F- and 31P-NMR reaction checks are recorded next morning.
The reaction solution is freed from CH2Cl2 and all volatile constituents in vacuo, leaving an orange oil.
Crude yield: 4.2 g (98.6% of theory
NMR data: in CD2Cl2














Nucleus
δ (ppm)
Splitting
Coupling
Assignment



















31P
−147.9
t, sept
1JPF = 870
—PF2(C2F5)3





2JPF = 89


19F
−94.4
d
1JPF = 870
—PF2(CF2CF3)3



−80.9
m

—PF2(CF2CF3)3 (6F)



79.8
m

—PF2(CF2CF3)3 (3F)



−113.0
m

—PF2(CF2CF3)3 (4F)



−113.3
m

—PF2(CF2CF3)3 (2F)


1H
7.92
d
3JHH = 7.0
DMAP (2H)



6.80
d
3JHH = 7.0
DMAP (2H)



4.13
q

—O—CH2CH3 (2H)



3.99
q

—O—(CH2)4—CH2— (2H)



3.26
s

DMAP (6H)



2.32
t
3JHH = 7.4
—O—(CH2)4—CH2—



1.62
m

C(O)— (2H)



1.53
m

—O—(CH2)4—CH2— (2H)



1.32
m

—O—(CH2)4—CH2— (2H)



1.27
t
3JH = 7.0
—O—(CH2)4—CH2— (2H)






—O—CH2—CH3 (3H)


13C
174.8
s

—C(O)—



157.5
s

DMAP



138.4
s

DMAP



107.1
s

DMAP



66.8
m

—O—CH2—(CH2)4—



60.5
s

—O—CH2CH3



40.0
s

DMAP



34.3
s

—O—CH2—CH2—



30.7
d
3JPC = 8.1
(CH2)3—



25.2
s

—O—CH2—CH2—



24.7
s

(CH2)3—



13.8
s

—O—CH2—CH2—






(CH2)3—






—O—CH2—CH2—






(CH2)3—






—O—CH2—CH3









Example 20
(C2F5)3PF2. DMAP with Ethanolamine




4.27 g (7.79 mmol) of (C2F5)3PF2. DMAP in 60 ml of dichloromethane are initially introduced in a 100 ml Schlenk flask under protective gas, and 0.48 g (7.79 mmol) of ethanolamine is added dropwise to the solution at 0° C. After the addition, the ice bath is removed, and the mixture is stirred at RT overnight. 19F- and 31P-NMR reaction checks are recorded next morning.
The reaction solution is then freed from CH2Cl2 and all volatile constituents in vacuo, leaving a slightly yellow powder.
Crude yield: 4.55 g (95.8% of theory)
NMR data: in CD2Cl2














Nucleus
δ (ppm)
Splitting
Coupling
Assignment



















31P
−148.4
t, sept
1JPF = 875
—PF2(C2F5)3





2JPF = 87


19F
−94.7
d
1JPF = 875
—PF2(CF2CF3)3



−81.3
m

—PF2(CF2CF3)3 (6F)



−80.0
m

—PF2(CF2CF3)3 (3F)



−113.3
m

—PF2(CF2CF3)3 (4F)



−113.5
m

—PF2(CF2CF3)3 (2F)


1H
8.00
d
3JHH = 5.2
DMAP (2H)



7.73
s, br

—NH2 (2H)



6.73
d
3JHH = 5.2
DMAP (2H)



4.15
m

—O—(CH2)—



3.19
s

NH2(2H)



2.94
m

DMAP (6H)



156.7
s

—O—(CH2)—



141.4
s

NH2(2H)


13C
106.9
s

DMAP



65.2
m

DMAP



41.8
d

DMAP



39.6
s
3JCP = 8.7
—O—CH2—CH2—






NH2






—O—CH2—CH2—






NH2






DMAP









Note:
If the reaction is carried out in DMF instead of in CH2Cl2, another isomer forms in which the two F atoms on the phosphorus are different.
Example 21
Reaction of (C2F5)3PF2. DMAP with 2-methoxyethanol




3.86 g (7.04 mmol) of (C2F5)3PF2. DMAP in 60 ml of dichloromethane are initially introduced in a 100 ml Schlenk flask under protective gas, and 0.54 g (7.04 mmol) of 2-methoxyethanol is added dropwise to the solution at 0° C. After the addition, the ice bath is removed, and the mixture is stirred at RT overnight. 19F- and 31P-NMR reaction checks are recorded next morning. The reaction solution is then freed from CH2Cl2 and all volatile constituents in vacuo, leaving a slightly yellow powder.
Crude yield: 4.38 g (99.8% of theory)
NMR data: in CD2Cl2














Nucleus
δ (ppm)
Splitting
Coupling
Assignment



















31P
−147.8
t, sept
1JPF = 878
—PF2(C2F5)3





2JPF = 89


19F
−94.8
d
1JPF = 878
—PF2(CF2CF3)3



−81.0
m

—PF2(CF2CF3)3 (6F)



−79.9
m

—PF2(CF2CF3)3 (3F)



−113.2
m

—PF2(CF2CF3)3 (4F)



−113.5
m

—PF2(CF2CF3)3 (2F)


1H
8.03
d
1JHH = 6.3
DMAP (2H)



6.75
d
1JHH = 6.3
DMAP (2H)



4.27
m

—O—(CH2)2—O—



3.62
m

CH3(2H)



3.32
s

—O—(CH2)2—O—



3.24
s

CH3(2H)



157.3
s

—O—CH3



139.3
s

DMAP (6H)


13C
106.6
s

DMAP



73.5
d
3JCP = 7.9
DMAP



65.6
m

DMAP



57.6
s

—O—CH2—CH2—



40.1
s

O—CH3






—O—CH2—CH2—






O—CH3






—O—CH3






DMAP









Example 22
Reaction of (C2F5)3PF2 with PMe3




(C2F5)3PF2 is dissolved in diethyl ether, and excess PMe3 is condensed on at −196° C. The reaction solution is warmed to room temperature and investigated by NMR spectroscopy.
31P{1H}-NMR spectroscopic data of the two conformers of [P(C2F5)3F2(PMe3)] in Et2O













δ, ppm
Multiplicity
J[Hz]
Assignment


















24.5
d, t, quin,
1J(PP) = 302
[P(C2F5)3F2(PMe3)] (IIa)



m
2J(PF) = 215




3J(PF) = 25


16.3
m
—
[P(C2F5)3F2(PMe3)] (IIIa)


−134.8
d, d, quin,
1J(PFA) = 923
[P(C2F5)3F2(PMe3)] (IIIa)



t, d
1J(PFB) = 853




2J(PF) = 102




2J(PF) = 76




1J(PP) = 53


−141.9
t, quin, t,
1J(PF) = 889
[P(C2F5)3F2(PMe3)] (IIa)



d
2J(PF) = 96




2J(PF) = 68




1J(PP) = 303









19F-NMR spectroscopic data of the two conformers of [P(C2F5)3F2(PMe3)] in Et2O














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−28.6
d, d, m
1J(PAF) = 885
PF (IIa)
2.2




2J(PBF) = 215


−29.6
d, m
1J(PAF) = 923
PFA (IIIa)
3.3


−60.0
d, d, m
1J(PAF) = 853
PFB (IIIa)
3.7




2J(PBF) = 140


−81.3
m
—
—
14.1


−81.7
m
—
—
16.2


−82.4
m
—
—
37.5


−103.9
m
—
—
9.8


−104.6
m
—
—
4.5


−105.7
m
—
—
8.9


−106.4
m
—
—
3.2


−107.5
m
—
—
0.5


−110.6
m
—
—
8.5


−114.7
m
—
—
4.3









Example 23
Reaction of (C2F5)2PF3 with PMe3




(C2F5)2PF3 is dissolved in diethyl ether, and excess PMe3 is condensed on at −196° C. The reaction solution is warmed to room temperature and investigated by NMR spectroscopy.
31P{1H}-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(PMe3)] in Et2O













δ, ppm
Multiplicity
J[Hz]
Assignment


















19.5
d, d, t, m
1J(PP) = 463
[P(C2F5)2F3(PMe3)] (IIb)




2J(PFA) = 268




2J(PFB) = 147


10.9
m
—
[P(C2F5)2F3(PMe3)] (Ib)


−139.2
d, t, d,
1J(PFA) = 907
[P(C2F5)2F3(PMe3)] (Ib)



quin
1J(PFB) = 956




1J(PP) = 71




2J(PF) = 118


−140.0
d, t, d, m
1J(PFA) = 949
[P(C2F5)2F3(PMe3)] (IIb)




1J(PFB) = 947




1J(PP) = 465




2J(PF) = 104









19F-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(PMe3)] in Et2O














δ, ppm
Multiplicity
J[Hz]
Assignment
Integral



















−21.9
d, d, m
1J(PAF) = 945
PFA (IIb)
0.3




2J(PBF) = 268


−48.6
d, m
1J(PF) = 907
PFA (Ib)
1


−70.5
d, d, m
1J(PF) = 957
PFB (Ib)
2




2J(FF) = 92


−72.2
d, d, d, m
1J(PF) = 948
PFB (IIb)
0.8




2J(PF) = 146




2J(FF) = 55


−80.4
m
—
CF3 (IIb)
1


−82.0
d, quar, d
3J(PF) = 21
CF3 (Ib)
6




4J(FF) = 5




4J(PBF) = 1


−82.4
m
—
CF3 (IIb)
1.1


−112.5
d, quar
2J(PF) = 119
CF2 (Ib)
4




3J(FF) = 15


−117.0
d, m
2J(PF) = 95
CF2 (IIb)
—


−118.1
d, m
2J(PF) = 105
CF2 (IIb)
—

## Claims

1. A compound formula I


[P(Rf)nF5-nD]−  I,


where
Rf in each case, independently of one another, denotes a straight-chain or branched fluoroalkyl group having 1 to 8 C atoms,
n denotes 1, 2 or 3 and
D denotes a Lewis base selected from triphenylphosphine oxide, trimethyl phosphate, aromatic amines, dialkyl ethers, aromatic or aliphatic tertiary phosphines, dialkylformamides, dialkylacetamides or N-alkyl-2-pyrrolidones, where said alkyl groups have, in each case independently of one another, 1 to 8 C atoms, or

a tautomer or stereoisomer thereof, including mixtures thereof in all ratios.

2. A compound according to claim 1, wherein D denotes an aromatic amine, a dialkyl ether, an aromatic or aliphatic tertiary phosphine, a dialkylformamide, a dialkylacetamide or an N-alkyl-2-pyrrolidone, where said alkyl groups have, in each case independently of one another, 1 to 8 C atoms.

3. A compound according to claim 1, wherein D denotes 4-dimethylaminopyridine or dimethylformamide.

4. A process for the preparation of compounds according to claim 1, said process comprising:
reacting a fluoroalkylfluorophosphorane of formula II


(Rf)nPF5-n  II,


where
Rf in each case, independently of one another, denotes a straight-chain or branched fluoroalkyl group having 1 to 8 C atoms and
n denotes 1, 2 or 3,

with a Lewis base D selected from triphenylphosphine oxide, trimethyl phosphate, aromatic amines, dialkyl ethers, aromatic or aliphatic tertiary phosphines, dialkylformamides, dialkylacetamides or N-alkyl-2-pyrrolidones, where said alkyl groups have, in each case independently of one another, 1 to 8 C atoms.

5. The process according to claim 4, wherein the perfluoroalkylfluoro-phosphorane is employed in excess.

6. A method for masking at least one OH group of an organic compound, comprising: reacting an organic compound having at least one OH group with a compound according to claim 1.

7. The method according to claim 6, wherein the organic compound having at least one OH group is an aliphatic or aromatic alcohol containing at least one OH group or is an oligomeric or polymeric compound containing at least one OH group.

8. The method according to claim 6, wherein the compound having at least one OH group is a polyol or a polyethylene glycol.

9. The method according to claim 7, wherein the compound having at least one OH group is a polyol or a polyethylene glycol.

10. The process according to claim 4, wherein the Lewis base is employed in excess.

11. A compound according to claim 1, wherein Lewis base D is triphenylphosphine oxide or trimethyl phosphate.

12. A compound according to claim 1, wherein Lewis base D is tri-phenylphosphine, diphenylmethylphosphine, trimethylphosphine, triethylphosphine, tri-i-propylphosphine, tributylphosphine, trihexylphosphine, or tri-cyclohexylphosphine.

13. A compound according to claim 1, wherein Lewis base D is trimethylphosphine.

14. A compound according to claim 1, wherein Lewis base D is dimethyl-formamide, diethylformamide, or dipropylformamide.

15. A compound according to claim 1, wherein Lewis base D is dimethylformamide.

16. A compound according to claim 1, wherein Lewis base D is dimethylacetamide, diethylacetamide, or dipropylacetamide.

17. A compound according to claim 1, wherein Lewis base D is N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, or N-butyl-2-pyrrolidone.

18. A compound according to claim 1, wherein Lewis base D is an aromatic amine or dialkylformamide.

19. A compound according to claim 1, wherein Lewis base D is 4-dimethylaminopyridine.

20. A compound according to claim 1, wherein Rf is CF3—CHF—CF2-, CF2H—CF2—, CF3—CF2—CH2—, CF3—CF2—CH2—CH2—, CF3—CF2—CF2—CF2—CF2—CF2—CH2—CH2—, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, n-nonafluorobutyl, sec-nonafluorobutyl, tert-nonafluoro-butyl, dodecafluoropentyl, 1-, 2- or 3-trifluoromethyloctafluorobutyl, 1,1-, 1,2- or 2,2-bis(trifluoromethyl)pentafluoropropyl, 1-pentafluoroethylhexafluoropropyl, n-tridecafluorohexyl, n-pentadecafluoroheptyl, or n-heptadecafluorooctyl.