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    • 专利摘要:
    The invention relates to a process for the preparation of ionic liquids based on the Bistriflimid anion, wherein in a first stage, a primary aliphatic amine R-NH2 is reacted with trifluoromethanesulfonic anhydride Tf20 to the corresponding N-alkylated Trifluormethansulfonsäureimid R-NTf2, which in a second Stu Fe is further reacted with a nucleophile Nu to form an ionic liquid consisting of the corresponding alkylated nucleophile R-Nu + as cation and the bis-triflimide anion Tf2N: Tf20 Nu ---- 3) 11o R-NTf2 ------ '3) 11o R-Nu + - NTf2 characterized in that a) in the first stage, an alkylamine having at least 3 carbon atoms dissolved in an organic solvent is used; b) in the second stage, a nitrogen heterocycle or a phosphorus compound is used as a nucleophile; and c) both stages are carried out in a continuous flow.
    公开号:AT518095A1
    申请号:T825/2015
    申请日:2015-12-30
    公开日:2017-07-15
    发明作者:Ing Dr Techn Katharina Bica Dipl；Dipl Ing Dr Techn Michael Schön (Fh)；Gärtner Peter；D Mihovilovic Marko
    申请人:Technische Universität Wien；
    IPC主号:
    专利说明:

    The present invention relates to a process for the preparation of ionic liquids based on the bis-triflimide anion.
    STATE OF THE ART
    Ionic liquids are defined as salts that are liquid at temperatures below 100 ° C. This is due to the fact that charge delocalization and steric effects hinder the formation of a stable crystal lattice, so that even the supply of low thermal energy is sufficient to overcome the lattice energy and break up the crystal lattice. Due to their vanishingly low volatility, high dissolving power for various organic and inorganic compounds, conductivity and non-flammability, ionic liquids have found a variety of applications in recent years. Common ionic liquids are based, inter alia, on alkylated imidazolium, pyridinium, pyrrolidinium, piperidinium, guanidinium, morpholinium, ammonium and phosphonium cations, while the anions are predominantly tetrafluoroborates, tri-fluoroacetates, hexafluorophosphates, phosphinates, p-toluenesulfonates (Tosylates), tri-fluoromethylsulfonate (triflates) and amides and imides thereof. The present invention is concretely concerned with the preparation of bis (trifluoromethane-sulfonyl) imides (bis-triflimides, NTf2 ') from positively charged nitrogen heterocycles and phosphorus compounds.
    For the preparation of such compounds, numerous synthetic methods are known. In most cases, ionic liquids based on bis-triflimides are prepared in a two-step process by preparing a quaternary ammonium or phosphonium salt, which is subsequently reacted by an ion exchange reaction with lithium bis-triflimide (LiNTf 2). The ionic liquids thus obtained must be purified by means of numerous extraction steps and are often contaminated with traces of halides and metals.
    Alternatively, first as a precursor, an N-alkyl triflimide by reacting an amine with trifluoromethanesulfonic anhydride Tf20 to the corresponding N-alkylated
    Trifluoromethanesulfonic acid imide R-NTf2, which can subsequently be further reacted with a nucleophile Nu to give the corresponding alkylated nucleophile R-Nu + as a cation and the bis-triflimide anion NTf2 ', also referred to herein as bistriflimidide. The following scheme illustrates such a two-step synthesis:
    The preparation of the precursor, ie the corresponding N-alkyltriflimide is disclosed, for example, in the following references. N-methylbistriflimide: Kübler et al., Dalton Trans. 2014, 43, 3750-3766.
    Zhang et al., Chem. Commun. 2003, 2334-2335. N-Benzylbistriflimid:
    Arvai et al., Tetrahedron 2009, 65, 5361-5368. N-butylbistriflimide: WO 2007/091817
    These reactions known to the literature for the corresponding N-alkyltriflimide require reaction times of at least 1 h at room temperature up to 12 h under reflux. However, the reaction of the corresponding amine R-NH2 with trifluoromethanesulfonic anhydride Tf2Ü is described only by Arvai et al. (see above) for benzylamine and in WO 2007/091817 for butylamine, while Kübler et al. (see above) methyl iodide with the silver salt of the bis-triflimide and Zhang et al. (see above) to react unsubstituted bis-triflimide with trimethyl orthoacetate to avoid photolysis of the silver salt.
    However, the latter two references also disclose the second stage, i. the reaction of the triflimide with the nucleophile Nu, namely Kübler et al. the reaction of N-methylbistriflimide into ferrocenyl-based ionic liquids, while Zhang et al. disclose the preparation of ionic liquids by reacting the N-methylbistriflimide with N-methylimidazole or pyridine to form the corresponding (doubly) methylated heterocycle as cation with the bis-triflimide anion as counterion, which, as mentioned at the beginning, is a very common reaction for the second stage represents.
    On the other hand, the production of ionic liquids in continuous flow in a tubular or capillary reactor instead of the usual batch process in a stirred reactor is less well-known in the literature. For this purpose, only - by Wilms et al., Org. Proc. Res. Dev. 2009, 13, 961-964, the reaction of optionally substituted phenylalkyl bromides with N-methylimidazole, by Waterkamp et al., Green Chem. 2007, 9, 1084-1090, the reaction of butyl bromide also with N -Methylimidazole, - von Löwe et al., Chem. Eng. J., 2009, 155, 548-550, the reaction of methyl triflate with 1,3-dimethylimidazole and - Renken et al., Chem. Eng. Proc. 2007, 46, 840-845, the reaction of diethyl sulfate with again N-methylimidazole disclosed.
    Although this results in very short reaction times in the range of a few minutes, the use of capillary reactors for the preparation of ionic liquids based on bis-triflimides is just as little known as their use for preparing the N-alkylated bis-triflimides as precursors.
    Against this background, the aim of the research work of the inventors was the development of a new, time-saving and therefore more economical process for the production of ionic liquids based on bistal triflimides.
    DISCLOSURE OF THE INVENTION
    This object is achieved by the present invention by providing a process for the preparation of ionic liquids based on the bis-triflimide anion, wherein in a first stage a primary aliphatic amine R-NH2 is reacted with trifluoromethanesulfonic acid anhydride Tf20 to give the corresponding N-alkylated trifluoromethanesulfonic acid imide R-NTf2 which is further reacted in a second step with a nucleophile Nu to form an ionic liquid consisting of the corresponding alkylated nucleophile R-Nu + as cation and the bis-triflimide anion Tf2N_:
    the process according to the invention being characterized in that a) in the first stage an organic amine-dissolved alkylamine having at least 3 carbon atoms is used; b) in the second stage, a nitrogen heterocycle or a phosphorus compound is used as a nucleophile; and c) both stages are carried out in continuous flow in a tube or capillary reactor.
    In fact, in the course of their research, the inventors have not only found that both steps of the above reaction are feasible in a capillary reactor, but also quite surprisingly, that with appropriate choice, the first stage operating parameters in continuous flow even at reaction times of only a few seconds, ie less than 1 minute, preferably in the range of about 30 seconds or less, and at temperatures around room temperature, e.g. at 20 ° C to 40 ° C, complete conversion of the amines to the N-alkylated Bistriflimiden can be achieved, which leads to excellent yields of the desired ionic liquids in the sequence. Without wishing to be bound by theory, the inventors believe that the reason for this lies in the good volume-surface ratio of the reaction mixtures in tubular and, in particular, capillary reactors, which is the result of exothermic reactions such as imidation between alkylamines and tri-fluoromethanesulfonic anhydride particularly strong. In combination with the reaction times of the second stage, which are also in the range of only a few minutes in the inventive use of Bistriflimiden, preferably less than 30 minutes, more preferably about 15 minutes or less, resulting total reaction times for both stages of only a few minutes. This represents a considerable time savings compared with the one or even several hours of reaction times required in the prior art alone for the first stage, which enormously increases the throughput when carrying out the overall reaction compared to current production processes.
    Moreover, the ionic liquids produced according to the present invention are neither contaminated with halides nor with metals.
    Since the economics of the process of the present invention would be severely limited by the increased equipment expense of using methylamine or ethylamine, both of which are gaseous at room temperature, they are not considered by the present invention to be alkylamines R-NH2, although their reactions are, of course, natural could also be carried out in an analogous manner. Namely, an essential advantage of the process according to the invention is that alkyl bistriflimides having different chain lengths can be varied in order to then react with the same nucleophile, e.g. N-methylimidazole or a phosphine to be converted to ionic liquids of different chain length.
    According to the present invention, the two stages can either be carried out in immediate succession without an intermediate step, or, after the first stage has been carried out, the solvent can be evaporated off, optionally the intermediate product, i. the N-alkylated bis-triflimide, and the second stage is carried out without solvent in bulk. The first variant of the consistently continuous process has the advantages of lower equipment cost and shorter total reaction time, however, it was in corresponding experiments in the presence of the solvent of the first stage, for which according to the present invention preferably dichloromethane (DCM) is used in the second stage to a Phase separation of the reaction mixture, resulting in a significant reduction in the second stage conversion. Therefore, according to the present invention, especially when using DCM, it is preferable to remove the solvent between the two stages.
    In the laboratory-scale illustrative examples disclosed herein, purification of the prepared bis-triflimide intermediates by distillation (Vigreux column or Kugelrohr) was also performed to demonstrate the efficiency of the second process step without the presence of potentially interfering starting or by-products. In the commercial practice of the process of this invention, after optimization of all process parameters, such intermediate purification may well be eliminated, which should result in significantly higher (i.e., presumably in the range of 90% or greater) yields of the N-alkylidene trimides of the first stage.
    The primary aliphatic amine is apart from the minimum of 3 carbon atoms, in order to avoid the increased expenditure on equipment when using methylamine and ethylamine, not particularly limited, so that as alkyl radicals any amines from propylamine, the unbranched, branched or cyclic and sometimes substituted can be replaced, provided that the imidation reaction of the first stage and the alkylation reaction of the nucleophile in the second stage are not disturbed, are replaceable, such as also substituted with phenyl or other aromatic alkyl radicals. However, due to considerations of solubility, molecular weight, and reactivity with the reactants of both stages, the primary aliphatic amine is preferably a C 3 -C 20 alkylamine, more preferably a C 4 -C 14 alkylamine which is unsubstituted in particularly preferred embodiments, especially butyl -, hexyl or tetradecylamine used.
    The nucleophile used in the present invention is preferably an optionally substituted pyrrolidine, pyridine or imidazole or a phosphine, more preferably an N-alkylimidazole, in particular N-methylimidazole, an N-alkylpyrrolidine, an alkylated pyridine or a trialkylphosphine, since with these nucleophiles already achieved very good results. For the alkyl or other substituents of the nucleophile, preferably the same options apply as for the primary aliphatic amine, although in these cases methyl and ethyl are expressly included.
    The first stage is preferably carried out at a temperature in the range of 20 to 40 ° C, since even at these low temperatures good yields can be achieved after very short reaction times and thus the energy consumption can be kept low. For the same reason, the second stage of the process according to the invention is preferably carried out at a temperature in the range of 80 to 120 ° C.
    EXAMPLES
    The present invention will be further described below by way of non-limitative examples.
    General procedure
    Both stages of the process according to the invention were each carried out in a microreactor "Syrris Africa" in the form of a glass chip with a PTFE capillary reactor with 1 ml reaction volume, which was equipped with 3 supply channels for the supply of reactants by means of a micropump.
    First Step - Imidation All imidization reactions were carried out in anhydrous dichloromethane (DCM) as a solvent in which the two reactants, i. the alkylamine and trifluoromethanesulfonic anhydride were dissolved. The alkylamine was added as a 1 M solution and trifluoromethanesulfonic anhydride as a 2.2 M solution, while pure solvent was added via the third channel to rinse the microreactor between the reactions of the individual examples. Both first stage feed solutions were pumped through the reactor at a rate of 1 ml / min (at 100 psi pressure), giving an average reaction time of 30 seconds.
    The solutions emerging from the reactor were analyzed by infrared spectrometer ("Mettler Toledo ReactIR 15") to follow the conversions to the desired product and collected and collected after passage of the spectrometer.
    After completion of the reaction, the collected organic layer was extracted 2x each with saturated NaHCO3 solution, twice with dilute hydrochloric acid and 2x with pure water, then dried over anhydrous Na2SO4, filtered and the solvent evaporated under reduced pressure to give the desired N-alkylated Bistrifli-mid, which was further purified by distillation (over a long Vigreux column or by Kugelrohr) to give each a colorless liquid was obtained.
    Second stage - alkylation
    The supply of the reactants, i. of N-alkylated bis-triflimide and nucleophile, to the micro reactor "Syrris Africa" was carried out by means of two programmable syringe pumps with the respective pumping rate in substance without solvent on two of the three channels of the chip (the third channel was sealed), after the reactor first to the desired Reaction temperature had been heated.
    After passage of the dead volume (1 ml DCM to rinse the microreactor), the product was collected in a glass vial. After complete reaction, unreacted starting materials were distilled off under high vacuum at 80 ° C, leaving the respective product as a colorless liquid.
    example 1
    Preparation of 3-butyl-1-methyl-imidazol-3-ium-bis (trifluoromethylsulfonyl) -imidide
    Example 1a Preparation of N-Butylbis (trifluoromethvlsulphonyl) imide (1)
    Bu-NH 2 Tf 2 O (1) n-Butylamine (11.0 g, 150 mmol, 1.0 equiv.) And diisopropylethylamine (DIPEA, 42.7 g, 330 mmol, 2.2 equiv.) On the one hand and trifluoromethanesulfonic anhydride (Tf 2 O; 93.1 g, 330 mmol, 2.2 eq.), On the other hand, were each dissolved in anhydrous DCM. The volumes of both reagent solutions were each adjusted to 150 ml and they were introduced via separate pumps into the microreactor, where the reaction was carried out at a temperature of 20 ° C for a mean reaction time of 30 seconds.
    Subsequent optimization of the reaction conditions revealed an optimum amine / TF2O ratio of 1.00: 2.05 equivalents, corresponding to flow rates of 1035 pl / min for the amine solution and 965 μΙ / min of the anhydride solution. Detection by IR spectrometer showed complete conversion of the amine to the bis-triflimide (1).
    Work-up and purification by distillation, as explained above in the general process description, in the present case by means of a long Vigreux column, gave a yield of the title compound (1) of 35.7 g (106 mmol, 71% of theory) of a colorless liquid. MW for C6H9F6NO4S2: 337.26 g / mol bp .: 72-74 ° C (13 mbar) 1 H-NMR (CDCl 3, 200 MHz), δ: 0.96 (t, J = 7.2 Hz, 3H), 1 , 36 (sext, J = 7.3Hz, 2H), 1.80 (quint, J = 7.8Hz, 2H), 3.93 (t, J = 8.1Hz, 2H). 13C-NMR (CDCb, 50 MHz), δ: 13.3 (q), 19.6 (t), 31.8 (t), 54.2 (t), 119.2 (q, J = 324Hz) ,
    Example 1b Preparation of 3-Butyl-1-methyl-1H-imidazol-3-ium-bis (trifluoromethylsulfonylimidide (2)
    (1) NMI (2) N -methylimidazole (NMI, 522 mg, 6.36 mmol, p = 1.030, flow rate 17.48 pl / min, 1.0 eq.) Was treated with bis-triflimide (1) from Example 1a (2 , 14 g, 6.36 mmol, p = 1.500, flow rate 49.22 pl / min, 1.0 eq) were reacted at a reaction temperature of 120 ° C within a reaction time of 15 min. Removal of unreacted educts under high vacuum gave the pure product (2) in very good yield (2.40 g, 5.72 mmol, 90% of th.) As a colorless liquid. MW for C10H15F6N3O4S2: 419.36 g / mol 1H-NMR (CDCl 3, 200 MHz), δ: 0.82 (t, J = 7.3Hz, 3H), 1.23 (sec, J = 7.5Hz, 2H ), 1.73 (quint, J = 7.5Hz, 2H), 3.80 (s, 3H), 4.04 (t, J = 7.4Hz, 2H), 7.21-7.30 (m , 2H), 8.49 (s, 1H). 13 C-NMR (CDCb, 50 MHz), δ: 12.8 (q), 19.0 (t), 31.6 (t), 35.8 (q), 49.5 (t), 119.6 (q, J = 321Hz), 122.3 (d), 123.5 (d), 135.4 (d).
    Example 2
    Preparation of 1-butyl-3-methylpyridin-1-bis-bis (trifluoromethylsulfonyl) imidide
    Example 2a - Preparation of N-butl-bis (trifluoromethvlsulfonyl) imide (1)
    The product of Example 1a was used.
    Example 2b - Preparation of 1-butl-3-methvlpuridine-1-ium-bis (trifluoromethvlsulfonyl) -imidide (31
    (1) 3MP (3) 3-Picoline (3-methylpyridine, 3MP, 578 mg, 6.21 mmol, p = 0.957, flow rate 20.14 μΙ / min, 1.0 eq) was extracted with bis-triflimide (1) Example 1a (2.09 g, 6.21 mmol, p = 1.500, flow rate 46.56 μΙ / min, 1.0 eq.) Was reacted at a reaction temperature of 120 ° C within a reaction time of 15 min. Removal of unreacted educts in a high vacuum gave the pure product (3) in very good yield (2.36 g, 5.48 mmol, 88% of theory) as a colorless liquid. MW for C12H16F6N2O4S2: 430.39 g / mol 1H-NMR (MeOD, 200 MHz), δ: 0.85 (t, J = 7.3Hz, 3H), 1.29 (sec, J = 7.5Hz, 2H ), 1.87 (quint, J = 7.6Hz, 2H), 2.48 (s, 3H), 4.44 (t, J = 7.6Hz, 2H), 7.74-7.86 (m , 1H), 8.22 (d, J = 8.0Hz, 1H), 8.52 (br, 2H). 13 C-NMR (MeOD, 50 MHz), δ: 12.8 (q), 17.9 (q), 18.9 (t), 33.1 (t), 61.7 (t), 119.6 (q, J = 321Hz), 127.6 (Py-5), 140.1 (Py *), 141.3 (Py *), 143.5 (Py *), 146.0 (Py *).
    Example 3
    Preparation of 1-butyl-3-methylpyridin-1-bis-bis (trifluoromethylsulfonyl) imidide
    Example 3a - Preparation of N-Butylbis (trifluororethylenethvlsulphonyl) imide (1)
    The product of Example 1a was used.
    Example 3b - Preparation of 1-Butyl-1-methylpirrolidin-1-ium-bis (trifluoromethylsulfonylimidide (4)
    (1) NMP (4) N-methylpyrrolidine (NMP, 514 mg, 6.04 mmol, p = 0.800, flow rate 10.71 μΙ / min, 1.0 eq) was treated with bis-triflimide (1) from Example 1 ( 2.04 g, 6.04 mmol, p = 1.500, flow rate 22.62 μΙ / min, 1.0 eq) were reacted at a reaction temperature of 80 ° C within a reaction time of 30 min. Removal of unreacted educts under high vacuum gave the pure product (4) in very good yield (2.18 g, 5.16 mmol, 85% of theory) as a colorless liquid. MW for C11H20F6N2O4S2: 422.41 g / mol 1H NMR (MeOD, 200 MHz), δ: 0.87 (t, J = 7.2Hz, 3H), 1.29 (sec, J = 7.4Hz, 2H ), 1.63 (quint, J = 8.0Hz, 2H), 1.98-2.25 (m, 4H), 2.90 (s, 3H), 3.10-3.26 (m, 2H ), 3.26-3.48 (m, 4H). 13 C-NMR (MeOD, 50 MHz), δ: 13.0, 19.3, 21.2, 25.4, 48.0, 64.3 (2 peaks), 119.7 (q, J = 321 Hz ).
    Example 4
    Preparation of 3-hexyl-1-methyl-1H-imidazol-3-bis-bis (trifluoromethylsulfonyl) -imidide
    Example 4a - Preparation of N-hexylbis (trifluoromethvlsulfonvhimide (5)
    Hex-NH 2 Tf 2 O 5 (5) n-Hexylamine (14.2 g, 140 mmol, 1.0 eq) and diisopropylethylamine (DIPEA, 39.8 g, 308 mmol, 2.2 eq) on the one hand and trifluoromethanesulfonic anhydride (Tf 2 O; 86.9 g, 308 mmol, 2.2 eq.), On the other hand, were each dissolved in anhydrous DCM. The volumes of both reagent solutions were each adjusted to 140 ml and they were introduced via separate pumps into the microreactor where the reaction was carried out at a temperature of 20 ° C for a mean reaction time of 30 seconds.
    A later optimization of the reaction conditions revealed an optimum amine to TF20 ratio of 1.00: 2.10 equivalents, corresponding to flow rates of 1022.5 pl / min for the amine solution and 977.5 μΙ / min of the anhydride solution. Detection by IR spectrometer showed complete conversion of the amine to the bis-triflimide (5).
    Work-up and purification by distillation, as explained above in the general process description, in the present case by means of a long Vigreux column, gave a yield of the title compound (5) of 36.6 g (100 mmol, 72% of theory) of a colorless liquid. MW for C8H13F6NO4S2: 365.31 g / mol bp.: 90-94 ° C (10 mbar) 1 H-NMR (CDCb, 200 MHz), δ: 0.90 (t, J = 6.5Hz, 3H), 1 , 17-1.47 (m, 6H), 1.81 (quint, J = 7.4Hz, 2H), 3.92 (t, J = 8.2Hz, 2H). 13 C-NMR (CDCb, 50 MHz), δ: 13.9 (q), 22.5 (t), 25.9 (t), 29.8 (t), 31.1 (t), 54.4 (t), 119.2 (q, J = 324Hz).
    Example 4b - Preparation of 3-hexyl-1-methyl-1H-imidazol-3-ium-bis (trifluoromethylsulfonylpimidide (6)
    (5) NMI (6) N -methylimidazole (NMI, 567 mg, 6.91 mmol, p = 1.030, flow rate 15.73 μΙ / min, 1.0 eq) was treated with bis-triflimide (5) from Example 4a (2, 52 g, 6.91 mmol, p = 1.413, flow rate 51.00 μΙ / min, 1.0 eq.) Was reacted at a reaction temperature of 120 ° C within a reaction time of 15 min. Removal of unreacted educts under high vacuum gave the pure product (6) in very good yield (2.86 g, 6.39 mmol, 93% of theory) as a colorless liquid. MW for C12H19F6N3O4S2: 447.42 g / mol 1H-NMR (MeOD, 200 MHz), δ: 0.76 (t, J = 6.4Hz, 3H), 1.08-1.33 (m, 6H), 1.75 (quint, J = 6.9Hz, 2H), 2.82 (s, 3H), 4.05 (t, J = 7.4Hz, 2H), 7.23-7.31 (m, 2H ), 8.53 (s, 1H). 13 C-NMR (MeOD, 50 MHz), δ: 13.5 (q), 22.0 (t), 25.4 (t), 29.7 (t), 30.7 (t), 35.9 (q), 49.8 (t), 119.6 (q, J = 321Hz), 122.3 (d), 123.6 (d), 135.5 (d).
    Example 5
    Preparation of 3-tetradecylmethyl-1H-imidazol-3-ium-bis (trifluoromethyl-sulfonyl) imidide
    Example 5a - Preparation of N-tetradecyl bis (trifluoromethylsulfonyl) imide (7)
    Tdec-NH 2 TfrO (7) n -tetradecylamine (23.5 g, 110 mmol, 1.0 eq) and diisopropylethylamine (DIPEA, 31.3 g, 242 mmol, 2.2 eq) on the one hand and triflic anhydride (Tf 2 O, 68.3 g , 242 mmol, 2.2 eq.), On the other hand, were each dissolved in anhydrous DCM. The volumes of both reagent solutions were each adjusted to 110 ml, and they were introduced into the microreactor via separate pumps, where the reaction was carried out at a temperature of 40 ° C for a mean reaction time of 30 seconds.
    Subsequent optimization of the reaction conditions revealed an optimum amine to TF20 ratio of 1.00: 2.05 equivalents, corresponding to flow rates of 1035 pl / min for the amine solution and 965 μΙ / min of the anhydride solution. Detection by IR spectrometer showed complete conversion of the amine to the bis-triflimide (7).
    Work-up and purification by distillation, as explained above in the general process description, in the present case by Kugelrohr distillation, gave a yield of the title Compound (7) of 37.2 g (77.9 mmol, 71% of theory) of a colorless liquid , MW for Ci6H2gF6N04S2: 477.53 g / mol
    Bp .: 130-150 ° C (oil bath, 0.001 mbar) 1 H NMR (CDCl 3, 200 MHz), δ: 0.89 (t, J = 6.5Hz, 3H), 1.14-1.52 (m , 22H), 1.82 (quint, J = 7.3Hz, 2H), 3.93 (t, J = 8.2Hz, 2H). 13 C-NMR (CDCl 3, 50 MHz), δ: 14.2 (q), 22.9 (t), 26.3 (t), 29.0 (t), 29.5 (t), 29.6 (t, 2 peaks), 29.7 (t), 29.8 (t, 4 peaks), 32.1 (t), 54.4 (t), 119.2 (q, J = 325Hz).
    Example 5b - Preparation of 1-Methyl-3-tetradecyl-1H-imidazol-3-ium-bis (trifluoromethysulfone-4-diimidide (8)
    (7) NMI (8) N -methylimidazole (NMI, 347 mg, 4.22 mmol, p = 1.030, flow rate 11.21 pl / min, 1.0 eq) was treated with bis-triflimide (7) from Example 5a (2, 02 g, 4.22 mmol, p = 1.207, flow rate 55.49 pl / min, 1.0 eq.) Was reacted at a reaction temperature of 120 ° C within a reaction time of 15 min. Removal of unreacted educts under high vacuum gave the pure product (8) in very good yield (2.22 g, 3.97 mmol, 94% of theory) as a colorless liquid. MW for C20H35F6N3O4S2: 559.63 g / mol 1H-NMR (MeOD, 200 MHz), δ: 0.82 (t, J = 6.3Hz, 3H), 1.08-1.38 (m, 22H), 1.81 (quint, J = 8.1Hz, 2H), 3.87 (s, 3H), 4.10 (t, J = 7.5Hz, 2H), 7.31 (d, J = 1.6Hz , 2H), 8.61 (s, 1H). 13 C-NMR (MeOD, 50 MHz), δ: 14.0 (q), 22.6 (t), 26.0 (t), 28.8 (t), 29.2 (t), 29.3 (t), 29.4 (t), 29.5 (t), 29.6 (t, 3 peaks), 30.0 (t), 31.9 (t), 36.1 (q), 50 , 0 (t), 119.8 (q, J = 321Hz), 122.3 (d), 123.7 (d), 135.7 (d).
    Example 6
    Preparation of trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) -imidide
    Example 6a - Preparation of N-tetradecyl bis (trifluoromethvlsulfonvnimide (7)
    The product of Example 5a was used.
    Example 6b - Preparation of trihexyl (tetradecvophosphonium bis (trifluoromethyl) sulfonylimidide (9)
    (7) THP (9)
    Trihexylphosphine (THP, 773 mg, 2.70 mmol, p = 0.830, flow rate 31.08 pl / min, 1.0 eq) was treated with bis-triflimide (7) from Example 5a (1.29 g, 2.70 mmol, p = 1.207, flow rate 35.62 pl / min, 1.0 eq.) were reacted at a reaction temperature of 120 ° C within a reaction time of 15 min. Removal of unreacted starting materials in a high vacuum gave the pure product (9) in very good yield (1.86 g, 2.43 mmol, 90% of theory) as a colorless liquid. MW for C34H68F6NO4PS2: 764.00 g / mol 1H-NMR (MeOD, 200 MHz), δ: 0.75-0.99 (m, 12H), 1.08-1.36 (m, 34H), 1, 36-1.72 (m, 16H), 1.94-2.18 (m, 6H). 13 C-NMR (CDCl 3, 50 MHz), δ: 13.8 (q), 14.1 (q), 18.6 (t), 21.4 (t), 22.3 (t), 22.5 (t), 28.8 (t), 29.2-30.6 (several t), 30.9 (t), 31.9 (t).
    This new compound made by the inventors for the first time represents a further aspect of the present invention.
    In any case, the above examples clearly demonstrate the advantages of the preparation process according to the invention over the prior art in the preparation of ionic liquids based on the bis-triflimide anion from corresponding amines and tri-fluoromethanesulfonic anhydride, namely very short reaction times with nevertheless high conversions, high variability in the Chain length of the alkyl radical and the total absence of contaminating halides and metals.
    权利要求:
    Claims (11)
    [1]
    1. A process for the preparation of ionic liquids based on the Bistriflimid anion, wherein in a first stage, a primary aliphatic amine R-NH2 is reacted with trifluoromethanesulfonic anhydride Tf20 to give the corresponding N-alkylated trifluoromethane-sulfonic acid imide R-NTf2, which in a second Reaction with a nucleophile Nu to form an ionic liquid consisting of the corresponding alkylated nucleophile R-Nu + as cation and the bis-triflimide anion Tf2N ':

    characterized in that a) in the first stage, an alkylamine having at least 3 carbon atoms dissolved in an organic solvent is used; b) in the second stage, a nitrogen heterocycle or a phosphorus compound is used as a nucleophile; and c) both stages are carried out in a continuous flow.
    [2]
    2. The method according to claim 1, characterized in that the reaction time of the first stage is less than 1 min, preferably about 30 s.
    [3]
    3. The method according to claim 1 or 2, characterized in that the reaction time of the second stage is less than 30 minutes, preferably about 15 minutes.
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that after carrying out the first stage, the solvent is evaporated and the second stage is carried out without solvent in substance.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that as a primary aliphatic amine, a C3-C2o-alkylamine, preferably a C4-Ci4-alkyl-amine, is used.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that an optionally substituted pyrrolidine, pyridine or imidazole or a phosphine is used as the nucleophile.
    [7]
    7. The method according to claim 6, characterized in that the nucleophile used is an N-alkylimidazole, an N-alkylpyrrolidine, an alkylated pyridine or a trialkylphosphine.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the first stage is carried out at a temperature in the range of 20 to 40 ° C.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that at least in the first stage dichloromethane is used as a solvent.
    [10]
    10. The method according to any one of the preceding claims, characterized in that the second stage is carried out at a temperature in the range of 80 to 120 ° C.
    [11]
    11. trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imideid of the following formula:

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    同族专利:
    公开号 | 公开日
    WO2017112972A1|2017-07-06|
    AT518095B1|2018-01-15|
    引用文献:
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    US20120022269A1|2008-12-12|2012-01-26|Mitsubishi Materials Electroic Chemicals Co., Ltd.|Fluorine-containing n-alkylsulfonylimide compound, manufacturing method therefor, and method of manufacturing an ionic compound|
    JP2013075896A|2011-09-16|2013-04-25|Mitsubishi Materials Corp|Ionic compound and method of producing the same|
    CN103387544A|2012-05-08|2013-11-13|海洋王照明科技股份有限公司|Preparation method of imidazole ionic liquid|
    JP2019516734A|2016-05-20|2019-06-20|武田薬品工業株式会社|Pain treatment|
    CN109776362B|2019-03-08|2022-02-15|如鲲新材料科技有限公司|Novel process of bisimide salt|
    法律状态:
    2021-08-15| MM01| Lapse because of not paying annual fees|Effective date: 20201230 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA825/2015A|AT518095B1|2015-12-30|2015-12-30|Process for the preparation of ionic liquids based on the bis-triflimide anion|ATA825/2015A| AT518095B1|2015-12-30|2015-12-30|Process for the preparation of ionic liquids based on the bis-triflimide anion|
    PCT/AT2016/060136| WO2017112972A1|2015-12-30|2016-12-27|Method for producing ionic liquids|
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