Patent Grant
8829188
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group having 1 to 8 C atoms, i.e. in the case of a perfluorinated alkyl group all H atoms of this alkyl group have been replaced by F. In the case of a partially fluorinated alkyl group having 1 to 8 C atoms, the alkyl group has at least one F atom, 1, 2, 3 or 4 H atoms are present and the other H atoms of this alkyl group have been replaced by F. Known straight-chain or branched alkyl groups are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl.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.
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.
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)]
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]
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
1J(PF) = 915
2J(PFcis) = 103
2J(PFtrans) = 84
19F-NMR spectroscopic data of [HDMAP][(C2F5)3PF2OC(O)CH3] in CD3CN
1J(PF) = 923
2J(PF) = 85
2J(PF) = 103
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC(O)CH3] in CD3CN
3J(HH) = 7
3J(HH) = 7
13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC(O)CH3] in CD3CN
2J(PC) = 18
a {1H}
b {19F}
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
1J(PF) = 893
2J(PFcis) = 98
2J(PFtrans) = 84
19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN
1J(PF) = 896
2J(PF) = 97
2J(PF) = 79
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN
3J(HH) = 7
3J(HH) = 7
13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OPh] in CD3CN
a {1H}
b {19F}
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
1J(PF) = 882
2J(PFcis) = 96
2J(PFtrans) = 78
19F-NMR spectroscopic data of [HDMAP]2[{P(C2F5)3F2O}2C6H4] in CD3CN
1J(PF) = 881
2J(PF) = 98
2J(PF) = 80
1H-NMR spectroscopic data of [HDMAP]2[{P(C2F5)3F2O}2C6H4] in CD3CN
3J(HH) = 8
3J(HH) = 8
Elemental analysis data of [HDMAP]2[{P(C2F5)3F2O}2C6H4]
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
1J(PF) = 869
2J(PF) = 88
19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN
1J(PF) = 869
2J(PF) = 83
2J(PF) = 86
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN
3J(HH) = 7
4J(PH) = 1
3J(PH) = 7
3J(HH) = 7
3J(HH) = 7
3J(HH) = 7
13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OEt] in CD3CN
3J(CP) = 10
a {1H}
b {19F}
Elemental analysis data of [HDMAP][P(C2F5)3F2OEt]
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
1J(PF) = 886
2J(PF) = 88
19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN
1J(PF) = 883
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN
3J(FH) = 9
3J(PH) = 4
3J(HH) = 7
13C-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OCH2CF3] in CD3CN
a {1H}
b {19F}
Elemental analysis data of [HDMAP][P(C2F5)3F2OCH2CF3]
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
1J(PF) = 873
1J(PF) = 88
19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3
1J(PF) = 876
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3
3J(HH) = 7
3J(HH) = 7
3J(HH) = 7
3J(HH) = 7
3J(HH) = 7
13C{1H}-NMR spectroscopic data of [HDMAP][P(C2F5)3F2ODec] in CDCl3
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]
1J(PF) = 871
2J(PF) = 86
19F-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC2H4OH]
1J(PF) = 873
2J(PF) = 83
1H-NMR spectroscopic data of [HDMAP][P(C2F5)3F2OC2H4OH]
3J(HH) = 4
3J(HH) = 4
3J(PH) = 4
3J(HH) = 8
3J(HH) = 8
13C-NMR spectroscopic data of [H DMAP][P(C2F5)3F2OC2H4OH]
2J(PC) = 9
a {1H}
b {19F}
Elemental analysis data of [HDMAP][P(C2F5)3F2OC2H4OH]
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
2J(PF) = 960
2J(PFcis) = 103
19F-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF
1J(PF) = 947
2J(PF) = 88
1H-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF
13C-NMR spectroscopic data of [P(C2F5)3F2(dmf)] in DMF
1J(CH) = 143
1J(CP) = 249
2J(CP) = 30
1J(CH) = 218
a {1H}
b {19F}
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
1J(PF) = 847
2J(PF) = 86
19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OH] in acetone-d6
1J(PF) = 839
2J(PF) = 85
1H-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OH] in acetone-d6
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
1J(PF) = 871
19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)3F2OEt] in DMF
1J(PF) = 871
2J(PF) = 83
2J(PF) = 86
(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
1J(PF) = 999
2J(PF) = 102
19F-NMR spectroscopic data of [P(C4F9)3F2(dmf)] in DMF a
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
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
1J(PF) = 903
2J(PF) = 88
19F-NMR spectroscopic data of H[P(C4F9)3F2OEt]. nDMF in DMF
1J(PF) = 899
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
1J(PFA) = 847
1J(PFB) = 922
2J(PF) = 95
3J(PH) = 7
1J(PFA) = 947
1J(PFB) = 986
2J(PF) = 108
19F-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF
1J(PFA) = 848
1J(PFA) = 948
1J(PFB) = 987
2J(FBFA) = 45
1J(PFB) = 922
2J(FBFA) = 46
2J(PF) = 95
2J(PF) = 108
3J(FFA) = 10
3J(FFB) = 11
2J(PF) = 93
1H-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF
13C-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(dmf)] in DMF
1J(CH) = 144
1J(CP) = 329
2J(CP) = 32
1J(CH) = 214
a {1H}
b {19F}
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
1J(PFA) = 910
1J(PFB) = 926
2J(PF) = 108
19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OH] in DMF
1J(PF) = 910
1J(PF) = 926
2J(FF) = 46
3J(PF) = 11
3J(FF) = 7
2J(PF) = 103
3J(FF) = 10
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
1J(PFA) = 860
1J(PFB) = 876
2J(PF) = 94
19F-NMR spectroscopic data of [H(dmf)n][P(C2F5)2F3OEt] in DMF
1J(PF) = 860
1J(PF) = 876
2J(FF) = 47
3J(PF) = 13
3J(FF) = 7
2J(PF) = 94
3J(FFA) = 16
3J(FFB) = 8
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
31P
1JPF = 879
2JPF = 87
19F
1JPF = 879
1H
3JHH = 7.0
3JHH = 7.0
13C
3JCP = 8.7
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
31P
1JPF = 870
2JPF = 89
19F
1JPF = 870
1H
3JHH = 7.0
3JHH = 7.0
3JHH = 7.4
3JH = 7.0
13C
3JPC = 8.1
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
31P
1JPF = 875
2JPF = 87
19F
1JPF = 875
1H
3JHH = 5.2
3JHH = 5.2
13C
3JCP = 8.7
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.
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
31P
1JPF = 878
2JPF = 89
19F
1JPF = 878
1H
1JHH = 6.3
1JHH = 6.3
13C
3JCP = 7.9
(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
1J(PP) = 302
2J(PF) = 215
3J(PF) = 25
1J(PFA) = 923
1J(PFB) = 853
2J(PF) = 102
2J(PF) = 76
1J(PP) = 53
1J(PF) = 889
2J(PF) = 96
2J(PF) = 68
1J(PP) = 303
19F-NMR spectroscopic data of the two conformers of [P(C2F5)3F2(PMe3)] in Et2O
1J(PAF) = 885
2J(PBF) = 215
1J(PAF) = 923
1J(PAF) = 853
2J(PBF) = 140
(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
1J(PP) = 463
2J(PFA) = 268
2J(PFB) = 147
1J(PFA) = 907
1J(PFB) = 956
1J(PP) = 71
2J(PF) = 118
1J(PFA) = 949
1J(PFB) = 947
1J(PP) = 465
2J(PF) = 104
19F-NMR spectroscopic data of the two conformers of [P(C2F5)2F3(PMe3)] in Et2O
1J(PAF) = 945
2J(PBF) = 268
1J(PF) = 907
1J(PF) = 957
2J(FF) = 92
1J(PF) = 948
2J(PF) = 146
2J(FF) = 55
3J(PF) = 21
4J(FF) = 5
4J(PBF) = 1
2J(PF) = 119
3J(FF) = 15
2J(PF) = 95
2J(PF) = 105
| Number | Date | Country | Kind |
|---|---|---|---|
| 10010828 | Sep 2010 | EP | regional |
| 10010829 | Sep 2010 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2011/004354 | 8/30/2011 | WO | 00 | 3/15/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/041431 | 4/5/2012 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6264818 | Heider et al. | Jul 2001 | B1 |
| 7094328 | Ignatyev et al. | Aug 2006 | B2 |
| 8211277 | Ignatyev et al. | Jul 2012 | B2 |
| 20040171879 | Ignatyev et al. | Sep 2004 | A1 |
| 20100004461 | Ignatyev et al. | Jan 2010 | A1 |
| 20120264946 | Ignatyev et al. | Oct 2012 | A1 |
| Number | Date | Country |
|---|---|---|
| 19846636 | Apr 2000 | DE |
| 03002579 | Jan 2003 | WO |
| 2008092489 | Aug 2008 | WO |
| 2011072810 | Jun 2011 | WO |
| Entry |
|---|
| International Search Report for PCT/EP2011/004354 dated Jan. 18, 2012. |
| Kampa et al. “The Synthesis of Tris(perfluoroalkyl)-phosphanes” Angewandte Chemie (International Ed. In English) vol. 34, No. 11, [1995], pp. 1241-1244. |
| Peter G. M. Wuts, Theodora W. Greene “Greene's Protective Groups in Organic Synthesis, 4th Edition” Wiley-Interscience (Dec. 2006) p. 279, p. 420. |
| Number | Date | Country | |
|---|---|---|---|
| 20130178628 A1 | Jul 2013 | US |
