Ionic liquids containing anions [n(cf3)2]-

FIELD: chemistry.

SUBSTANCE: present invention concerns the salts containing bis(trifluoromethyl)imide anions and saturated, partially or completely unsaturated heterocyclic cations, method of production and application thereof as ionic liquids.

EFFECT: production of new salts to be used as ionic liquids.

19 cl, 5 ex

 

The present invention relates to salts containing anions bis(trifluoromethyl)imide and saturated, partially or fully unsaturated heterocyclic cations, to methods for their preparation and to their use as ionic liquids.

Ionic liquids or liquid salts are the kinds of ions, which consist of an organic cation and, typically, an inorganic anion. They do not contain any neutral molecules and have melting points below 373 K. In the field of technology there are many compounds that are used as ionic liquids. In particular, they are also objects of a number of patents and patent applications.

Thus, ionic liquids, solvent free, were revealed for the first time Hurley and Wier in a number of U.S. patents (US 2446331, US 2446339 and US 2446350). These salts that melt at room temperature consisted of AlCl3and a number of Gulidov n-alkylpyridine.

US 5827602 describes hydrophobic ionic liquids, which have a wide electrochemical window, for use as electrolytes in batteries. Such salts contain certain 5 - or 6-membered heterocyclic polynuclear cations and anions, with van-der-wallsof radius higher than 100 Å3for example halogenated alkylsulfonyl, mono - or Divertissement, fluorinated alkylphosphate.

In addition, the recently published some review articles (R.Sheldon "Catalytic reactions in ionic liquids", Chem. Commun., 2001, 2399-2407; M.J.Earle, K.R.Seddon "Ionic liquids. Green solvent for the future", Pure Appl. Chem., 72 (2000), 1391-1398; P.Wasserscheid, W.Keim "lonische Flüssig-keiten-neue Lösungen für die Übergangsmetallkatalyse" [Ionic Liquids - Novel Solutions for Transition-Metal Catalysis], Angew. Chem., 112 (2000), 3926-3945; .Welton "Room temperature ionic liquids. Solvents for synthesis and catalysis", Chem. Rev., 92 (1999), 2071-2083; R.Hagiwara, Ya. Ito "Room temperature ionic liquids of alkylimidazolium cations and fluoroanions". Journal of Fluorine Chem., 105 (2000), 221-227).

EP 1081129 reveals stable salts of N(CF3)2-containing the tetraalkylammonium and comparable cations. Not been described or heterocyclic cations or use of the described compounds as ionic liquids.

Properties of ionic liquids, such as melting point, thermal and electrochemical stability, viscosity, are influenced by the nature of the anion. In contrast, the polarity and hydrophilicity or lipophilicity can be varied by appropriate choice of the pair cation/anion. Thus, there is a need for new ionic liquids with various properties, which improve additional features on their application.

The present invention is to provide a new stable compounds with valuable properties, which can be used as ionic liquids, as well as the way they are received.

This problem is solved by providing salt on the cabbage soup formulas (1)

which contain the anion bis(trifluoromethyl)imide and saturated, partially or fully unsaturated heterocyclic cation.

In the formula

X is N, P, O or S,

n means an integer selected from 0, 1 or 2 such that X is saturated in accordance with its valency, increased by 1

And means saturated, partially or fully unsaturated hydrocarbon chain containing from 3 to 8 members,

in which all carbon atoms except one, can be replaced by identical or different heteroatoms selected from N, P, O or S,

where the carbon atoms of the hydrocarbon chain and present there heteroatoms are saturated substituents R2in accordance with their valences,

R1, R2mean-N provided that not formed a connection with positively charged heteroatom,

alkyl with non-branched chain or branched, containing from 1 to 20 carbon atoms,

alkenyl with non-branched chain or branched, containing from 2 to 20 carbon atoms and one or more double bonds,

quinil with non-branched chain or branched, containing from 2 to 20 carbon atoms and one or more triple relations,

saturated, partially or fully unsaturated cycloalkyl containing from 3 to 7 the volume of carbon

halogen, in particular fluorine or chlorine, provided that for X=N, O, S is not formed due halogen heteroatom,

-NO2provided that it is not formed due to positively charged heteroatom,

-CN, provided that it is not formed due to positively charged heteroatom,

where R2and/or R1in different and/or identical provisions heterocyclic rings are in each case identical or different,

where R2and/or R1can be connected to each other in pairs by a single or a double bond,

where one or more R2and/or R1can be partially or fully substituted by Halogens, in particular-F and/or-Cl, or partially by CN or-NO2provided that not all R2and R1are fully halogenated,

and where one or two carbon atoms, R2and/or R' may be replaced by heteroatoms and/or atomic groups selected from the group of-O-, -C(O)-, C(O)O-, -S-, -S(O)-, -SO2-, -SO2O-, -N=, P=, -NH-, -PH-, -NR'- and-PR'-, where R' represents a non-fluorinated, partially or perfluorinated C1-C6alkyl or-C6F5where the α-position, R1not substituted for X=O, S.

For the purposes of the present invention, the valence atom is taken to denote the number of links emanating from a neutral atom, or the number of electron pairs, catalytically atom shares with other atoms in the molecule, and which is represented as a dash valence in a simplified representation of the e-formulas. In accordance with the invention, the atoms of nitrogen and phosphorus thus have valency 3, oxygen atoms and sulfur valence 2, and the carbon atoms is the valency of 4. Phosphorus atoms can, if they are neutral atoms of the cation can have a valence of 5.

For the purposes of the present invention fully unsaturated compounds or substituents also taken to mean aromatic compounds or aromatic substituents.

Compounds in accordance with the invention are salts which contain the anion N(CF3)2-and as cation - heterocyclic ring containing from 4 to 9 members, which is saturated or unsaturated. Acceptable heteroatoms in it are N, P, O or S. in Addition to the heteroatom with a positive charge, a heterocyclic ring may also contain additional, identical or different heteroatoms selected from the group N, P, O or S; however, the ring contains at least one carbon atom.

Acceptable cations in accordance with the invention are heterocyclic compounds that are stable, in particular, those that can be isolated.

Each of the atoms of the heterocyclic rings are not the et as many identical or different substituents R 2or R1that they are saturated in accordance with their valences. In the case of a positively charged heteroatom number of the substituents corresponds to the valency increased by 1.

Some examples are given below, they are designed to confirm the number of substituents on the ring atom in accordance with the invention: monounsaturated or aromatic, i.e. sp2-hybridisable, carbon atoms have one Deputy, while saturated, sp3-hybridisable, the carbon atoms have two Deputy. The atoms of oxygen or sulfur, with a positive charge, which are connected in a cyclic ring via a double bond, do not have deputies, exactly the same as the atoms of oxygen or sulfur, having a positive charge, which are connected in a cyclic ring through a single bond, and atoms of nitrogen or phosphorus that do not have a positive charge, which are connected in a cyclic ring with the double bond. The atoms of oxygen or sulfur, with a positive charge, which are connected in a cyclic ring through a single bond, atoms of nitrogen or phosphorus, with a positive charge, which are connected in a cyclic ring via a double bond, and the atoms of nitrogen or phosphorus that do not have a positive charge, which are connected in a cyclic ring through Odin the telecommunication, have one Deputy.

With the exception of hydrogen acceptable substituents R1, R2heterocyclic rings are in accordance with the invention: C1-C20-in particular, With1-C12alkyl group, a C2-C20-in particular, With1-C12calsenilin or alkyline group, saturated or unsaturated, i.e. also aromatic, With3-C7cycloalkyl group, NO2CN or halogen. For halogen free, however, the limitation is that they are substituents only on carbon atoms or phosphorus atoms of the heterocyclic rings, but they are not substituents on the heteroatoms N, O, S, H, NO2and CN positively charged heteroatom.

The substituents R1, R2can also be contacted in pairs so that there are bi - or polycyclic cations. The substituents may be partially or completely replaced by halogen atoms, in particular-F and/or Cl, or partially by CN or NO2and contain one or two heteroatom or atomic group selected from the group O, S(O), C(O)O, S, S(O), SO2, SO2O, N, P, NH, PH, NR', PR'. However, in the case of complete halogenation not all present, the substituents R1and R2can be fully halogenated, i.e., at least one R1and/or R2is not Perg is loganianum.

Without limiting the generality of the examples of the substituents of heterocyclic cation in accordance with the invention are:

-F, -Cl, -Br, -I, -CH3- 2H5- 3H7, -CH(CH3)2- 4H9- (CH3)3- 5H11- 6H13- 6H13, -C7H15, -C8H17, -C9H19- 10H21- 12H25- 20H41, -Och3, -Och(CH3)2, -CH2OCH3- 2H4OCH(CH3)2, -SCH3, -SCH(CH3)2, -C2H4SC2H5- 2H4SCH(CH3)2, -S(O)CH3, -SO2CH3, -SO2C2H5, -SO2With3H7, -SO2CH(CH3)2, -CH2SO2CH3, -OSO2CH3, -OSO2CF3, -CH2N(H)C2H5- 2H4N(H)2H5, -CH2N(CH3)CH3, -C2H4N(CH3)CH3, -N(CH3)2, -N(CH3)3H5, -N(CH3CF3O-C4H8-O-C4H9, -S-C2H4-N(C4H9)2, -OCF3, -S(O)CF3, -SO2CF3, CF3, -C2F5- 3F7, -C4F9- (CF3)3, -CF2SO2CF3, -C2F4N(C2F5)C2F5, -CF=CF2 - (CF3)=CFCF3, -CF2CF=CFCF3, -CF=CFN(CF3CF3, -CFH2, -CHF2, -CH2CF3- 2F2H3- 3FH6, -CH2With3F7- (CFH2)3, -Cho, -C(O)HE, -CH2(O)HE, -CH2C(O)CH3, -CH2With(O)2H5, -CH2C(O)och3CH2S(O)OS2H5-C(O)CH3-C(O)och3,

In accordance with model calculations of the anion [N(CF3)2]-has van-der-wallsof radius 90,90 Å3and is thus relatively smaller compared to the anions of ionic liquids known in the prior art.

Salt in accordance with the invention are hydrophobic, meaning they are at least to some extent mixed with water.

Cu is IU, salt in accordance with the invention are very soluble in organic solvents.

In comparison with the known liquid salts salts in accordance with the invention have unusually low viscosity.

Salt in accordance with the invention are mostly stable. They can be isolated and stored at room temperature.

In addition, salts in accordance with the invention are relatively easier to obtain, while, in particular, the anion [N(SO2CF3)2]-known from the prior art, is obtained in difficulties, and he, in particular, is very expensive.

In the salts, which are preferred in accordance with the invention, the cation contains a heterocyclic saturated or unsaturated five-, six - or semiline ring. Example of five-membered rings in accordance with the invention, which contains only one carbon atom, represents a cation of tetrazole, for example,

In another preferred embodiment, the salts in accordance with the invention, the heterocyclic ring of the cation contains up to 3 heteroatoms selected from N, P, O or S. In the case of many of the heteroatoms is especially preferred that only a maximum of 2 heteroatoms were located in direct the hinnon neighborhood.

In addition to hydrogen atoms, the preferred substituents of the heterocyclic ring are halogen, in particular fluorine, provided that they are not linked with a heteroatom, with the exception of phosphorus, unbranched or branched C1-C6alkyl groups, in particular-CH3- 2H5, -n-C3H7, -CH(CH3)2, -n-C6H13and unbranched or branched, partially or perfluorinated C1-C6alkyl groups, in particular-CF3, -C2F5, -C4F9.

The preferred embodiment of the invention is a salt in which saturated, partially or fully unsaturated heterocyclic cation represents a five - or six-membered ring, which has the following structure:

where X is selected from the group N, P, O and S,

Y in each case independently selected from the group of C, N, P, O and S,

where at least one Y represents a carbon atom, while the remaining three or four Y can be carbon or heteroatoms.

The number of substituents R1on positively charged heteroatom X corresponds to the valency increased by 1, i.e. unsaturated oxygen atoms or sulfur does not have substituents, saturated with the s atoms of oxygen and sulfur, like unsaturated atoms of nitrogen and phosphorus, have one substituent R1and saturated atoms of nitrogen and phosphorus are two of the substituent R1.

The remaining atoms (Y) heterocyclic rings each has as many (m) identical or different substituents R2that they are saturated in accordance with their valences, i.e. saturated oxygen atoms and sulfur, like unsaturated atoms of nitrogen and phosphorus do not have substituents, saturated atoms of nitrogen and phosphorus, as unsaturated, sp2-hybridisable, the carbon atoms have one substituent R2and rich, sp3-hybridisable, the carbon atoms have two Deputy R2.

The substituents R1and R2are defined as in General formula (1).

In this embodiment, particular preference is given to variants in which the heteroatoms saturated or unsaturated five - or six-membered ring of the cation is distributed in such a way that the cation is selected from the following groups:

where X is selected from the group N, P, O and S, a Y in each case independently selected from the group of C, N, P, and S. the Numbers n, m of the substituents R1, R2on positively charged heteroatom X or the remaining atoms of the heterocyclic ring are determined in accordance with the General formulas for the five - or six-membered rings of the cations. The substituents R1and R2are defined as in General formula (1).

Without limiting the generality of the examples of such cations in accordance with the invention, containing five - or six-membered ring, are

where the substituents R are defined independently from each other, like R1and R2in the General formula (1),

and

In a further preferred variant of salt in accordance with the invention contain saturated, partially or fully unsaturated heterocyclic cation, which contains precondensation ring, i.e. the cation, in which two adjacent substituent of the heterocyclic ring are connected to each other, and selected from the following groups:

where X in each case independently selected from the group N, P, O, S, and s, where at least one X=N, P, O or S.

Every atom of the heterocyclic ring has as many (n) identical or different substituents R1that he is rich according to their valence, where n is incremented by 1 for heteroatom X carrying positive dawn is.

And' matter saturated, partially or fully unsaturated hydrocarbon chain containing from 2 to 7 members, where the carbon atoms of the hydrocarbon chain is saturated substituents R2in accordance with their valences.

The substituents R1and R2defined as in General formula (1), but where the substituents R1in the α-position relative to the positively charged heteroatom not have a methylene group in the immediate neighborhood of the heterocyclic ring.

Without limiting the generality of the examples of such cations in accordance with the invention are

Preference is also given to the salts in accordance with the invention, in which saturated, partially or fully unsaturated heterocyclic cation has the following structure:

where X is selected from the group of N and P, a Y is selected from the group N, P, O and S.

The number n of the substituents R1on the heteroatom Y is 0 in the case of an atom of oxygen or sulfur and equal to 1 in the case of an atom of nitrogen or phosphorus.

And' matter of the hydrocarbon chain, containing the th from 2 to 7 members. In' is a hydrocarbon chain containing from 1 to 6 members, where the hydrocarbon chains are saturated, partially or fully unsaturated, and in which all the carbon atoms independently from each other may be replaced by identical or different heteroatoms selected from N, P, O and S, and where the carbon atoms of the hydrocarbon chains And' and' are saturated substituents R2in accordance with their valences.

The substituents R1and R2are defined as in General formula (1). Without limiting the generality of the examples of such cations in accordance with the invention are

The present invention secondly relates to the salts of the General formula (2)

which contain the anion bis(tryptomer)imide and saturated or unsaturated heterocyclic shall ication, that is, a heterocyclic ring containing from 4 to 9 members, which is saturated or unsaturated and contains two positively charged heteroatom.

In this formula:

X, Y each independently of the other mean N, P, O or S,

n, m means an integer selected from 0, 1 or 2 such that each X and Y is saturated in accordance with its valency, increased by 1

A", B" means saturated, partially or fully unsaturated hydrocarbon chain containing from 0 to 4 members,

in which the carbon atoms may be replaced by identical or different heteroatoms selected from N, P, O and S,

where at least one carbon atom is present in the circuits a and B", taken together, and

where the carbon atoms of the hydrocarbon chains And" and" and the heteroatoms present there are saturated substituents R2in accordance with their valences,

R1, R2, R3mean-N, provided that not formed a connection with positively charged heteroatom,

alkyl with non-branched chain or branched, containing from 1 to 20 carbon atoms,

alkenyl with non-branched chain or branched, containing from 2 to 20 carbon atoms and one or more double bonds,

quinil with non-branched chain or branched, containing from 2 is about 20 carbon atoms and one or more triple relations, saturated, partially or fully unsaturated cycloalkyl containing from 3 to 7 carbon atoms,

halogen, in particular fluorine or chlorine, provided that for X=N, O, S is not formed due halogen heteroatom,

-NO2provided that it is not formed due to positively charged heteroatom,

-CN, provided that it is not formed due to positively charged heteroatom,

where R1, R2and/or R3in different and/or identical provisions heterocyclic rings are in each case identical or different,

where R1, R2and/or R3can be connected to each other in pairs by a single or double bond,

where one or more R1, R2and/or R3can be partially or fully substituted by Halogens, in particular-F and/or-Cl, or partially by CN or-NO2provided that not all R1, R2and R3are fully halogenated,

and where one or more carbon atoms, R1, R2and/or R3may be replaced by heteroatoms and/or atomic groups selected from the group of-O-, -C(O)-, C(O)O-, -S-, -S(O)-, -SO2-, -SO2O-, -N=, P=, -NH-, -PH-, -NR'-and-PR'-, where R' represents a non-fluorinated, partially or perfluorinated C1-C6alkyl or C6F5where α-R1and R3not substituted for X=O, S and Y=O, S

where the heterocyclic dication is a 4-, 5-, 6-, 7-, 8 - or 9-membered ring.

In the preferred salts of the dication is heterocyclic, saturated or unsaturated five-, six - or semiline ring.

Without limiting the generality of the examples of such dications in accordance with the invention are

The present invention also relates to the salts of the General formula (3)

,

which contain the anion bis(trifluoromethyl)imide and saturated, partially or fully unsaturated heterocyclic cation, six-membered heterocyclic ring which does not contain carbon atoms.

In this formula:

X, Y each independently of the other mean N, P, O or S,

n means an integer selected from 0, 1 or 2 such that X is saturated in accordance with its valency, increased by 1

m means an integer selected from 0, 1 or 2 so that Y is saturated in accordance with its valency,

R1, R2mean-N provided that not formed a connection with positively charged heteroatom,

alkyl with non-branched chain or branched, containing from 1 to 20 carbon atoms,

alkenyl with non-branched chain or branched, containing from 2 to 20 carbon atoms and one or more double bonds,

quinil with non-branched chain or branched, containing from 2 to 20 carbon atoms and one or more triple relations,

saturated, partially or fully unsaturated cycloalkyl containing from 3 to 7 carbon atoms,

halogen, in particular fluorine or chlorine, provided that for X=N, O, S is not formed due halogen heteroatom,

-OR, provided that the substituted heteroatom is O or S, where R2and/or R1in different and/or identical provisions heterocyclic rings are in each case identical or different,

where R2and/or R1can be connected to each other in pairs by a single or a double bond,

where one or more R2and/or R1can be partially or fully substituted by Halogens, in particular-F and/or-Cl, or partially by CN or-NO2provided that not all R2and R1are fully halogenated,/p>

and where one or more carbon atoms, R2and/or R1may be replaced by heteroatoms and/or atomic groups selected from the group of-O-, -C(O)-, C(O)O-, -S-, -S(O)-, -SO2-, -SO2O-, -N=, P=, -NH-, -PH-, -NR'- and-PR'-, where R' represents a non-fluorinated, partially or perfluorinated C1-C6alkyl or-C6F5where the α-position, R1not substituted for X=O, S.

Without limiting the generality of the examples of such cations in accordance with the invention are

It was found that the compounds according to the invention can easily be synthesized under mild conditions. Salt in accordance with the invention can be isolated with high yield.

To this end, the compounds of General formula

RFSO2N(CF3)2or RFC(O)N(CF3)2

where RF=F or CpF2p+1where p=1-8,

subjected to reaction with a fluoride of an alkali metal General formula DF, where D is selected from the group of alkali metals, in a polar organic solvent, and sequentially or simultaneously added salt of General formula (4)

or salt of the General formula (5)

which contains a saturated, partially and fully unsaturated heterocyclic mono - or dication, containing from 4 to 9 members, and the anion E-selected from the group of F-, Cl-, Br-I-BF4-, ClO4-AsF6-, SbF6-, SbCl6-PF6-, RFSO3-, FSO3-, (RF)2P(O)O-, RFP(O)2O-, RSO3-, ROSO3-, 1/2SO32-CN-, SCN-, RFC(O)O-RC(O)O-, 2,4-dinitrophenol and 2,4,6-trinitrophenol, where RFrepresents a perfluorinated C1-C6alkyl group or a perfluorinated aryl group, and R represents a C1-C6alkyl group or aryl group.

The heteroatoms X and Y, the numbers m and n, the hydrocarbon chain And a" and b" and the substituents R1, R2and R3salts of the General formula (4) or (5) are defined here as those defined for the General formula (1) and (2).

In this reaction bis(trifluoromethyl)amide peralkaline sulfonic acid is preferably used for the reaction with a fluoride of an alkali metal.

In a variant, which is preferred in accordance with the invention, the method is carried out as a reaction in the same vessel, that is, the intermediate compound obtained from the fluoride of the alkali metal and bis(trifluoromethyl)amide peralkaline sulphonic is iSlate or acerbis(trifluoromethyl)amide, not isolated, but instead is subjected to reaction directly with the salt of General formula (4) or (5). The reagents are preferably used in approximately equimolar amounts, when using acerbis(trifluoromethyl)amide is used in dual equimolar amounts.

If the salt has the General formula (4) or (5) is used in the form of fluoride, that is, if E-=F-the reaction in accordance with the invention can be carried out in one reaction vessel and without added fluoride of an alkali metal DF.

Is it possible the formation of volatile by-products are then removed under reduced pressure. Usually, however, produces by-products which are insoluble in the solvent, is separated by filtering. The solvent is removed, if it is desirable, together with volatile byproducts under reduced pressure. Salt in accordance with the invention can generally be isolated with a yield of over 80%.

In order to improve the purity, if it is low, salt in accordance with the invention can be dissolved in a polar organic solvent and subjected to imida rubidium Rb+N(CF3)2-. Formed and precipitated in the sediment salt of rubidium then filtered and rest ritel removed under reduced pressure.

The fluoride of the alkali metal used in accordance with the invention, is preferably a fluoride, potassium or rubidium, particularly preferably to use a less expensive potassium fluoride.

Polar organic solvent, which is preferred in accordance with the invention is chosen from the group of acetonitrile, dimethoxyethane, dimethylformamide and propionitrile.

The reaction in accordance with the invention is preferably carried out at a temperature from -40°C to 80°C, in particular from 0°C to 40°C., and very preferably at room temperature.

All connections in accordance with the invention have colpotomy nature, relatively low melting point (usually below 100°C) and can be used as ionic liquids.

Salt in accordance with the invention can be used as solvents for many synthetic or catalytic reactions, for example, acylation and alkylation Friedel -, cycloaddition Diels-alder reaction, reactions of hydrogenation and oxidation reactions Hake. In addition, fluorinated solvents, for example, can be synthesized for secondary and primary batteries.

They are acceptable as reagents for the introduction of groups N(CF3)2. For example, group N(CF3)2can Sames the te-halogen atoms in organic compounds by halogen. In addition, salts in accordance with the invention are of interest as precursors to obtain liquid-crystalline compounds and active ingredients, in particular for drugs and agents for plant protection.

The use of compounds in accordance with the invention as a non-aqueous electrolyte, if it is desired, in combination with other electrolytes known to the person skilled in the art, is also possible.

In addition, salts in accordance with the invention can be used as non-aqueous polar substances within acceptable reactions as phase transfer catalysts or as a medium for the homogeneous hydrogenation catalysts.

The complete disclosure content of all applications, patents and publications mentioned above are introduced in this application for illustrative purposes.

Even in the absence of additional comments it is assumed that the person skilled in the art will be able to utilize the above description in a broader scope. Preferred embodiments and examples are therefore to be illustrative description, which absolutely does not limit the invention in any way.

All NMR spectra were measured on a spectrometer Bruker Avance 300 (1N: 300,13 MHz,19F: 282,40 MHz).

Example 1

A solution of 2.93 g (12.3 mmole) Rb+N(CF3)2-that was received from 1.29 g (12.3 mmole) RbF and 3,63 g (12.7 mmole) CF3SO2N(CF3)210 cm3dry acetonitrile was added at room temperature with stirring to a solution of 2.15 g (12.3 mmole) chloride 1-butyl-3-methylimidazole 5 cm3dry acetonitrile. The reaction mixture was stirred at room temperature for 15 minutes, precipitated in the sediment RbCl was filtered and washed with dry acetonitrile (2×5 cm3). The acetonitrile was removed under vacuum to 120 PA, and the residue was dried for 2 hours at a temperature of 50°C at reduced pressure, thus obtaining 3,24 g butter-like substances.

The yield of bis(trifluoromethyl)imide 1-butyl-3-methylimidazole, [C8H15N12]+N(CF3)2-amounted to 90.5 per cent.

19F-NMR (standard: CCl3F; solvent: CD3CN): -37,35

1H-NMR (standard: tetramethylsilane was; solvent: CD3CN): 0,93 t (CH3); 1,32 m (CH2); 1.83 m (CH2); with a 3.87 (CH3); 4,17 t (CH2); 7,46 DD (CH); 7,51 DD (CH); the remaining 9.08 CL (CH); J3n,n=7,3 Hz; J3n,n=7,4 Hz; JNN=1,8 Hz

Example 2

The solution 4,65 g (19.6 mmole) Rb+N(CF3)2-that was received from 2,05 g (19.6 mmole) of RbF and 5,95 g (of 20.9 mmole) CF3SO2N(CF3) 220 cm3dry acetonitrile was added at room temperature with stirring to a solution of 3.65 g (18,8 mmole) bromide N-methyl-N-ethylpyrrolidin 20 cm3dry acetonitrile. The reaction mixture was stirred at room temperature for 15 minutes, precipitated in the sediment RbBr was filtered and washed with dry acetonitrile (2×5 cm3). The acetonitrile was removed under vacuum of 1.4 PA and the residue was dried for 2 hours at a temperature of 60-65°C. under reduced pressure, to thereby obtain 4.68 g of solids. The melting point of 80-85°C.

The yield of bis(trifluoromethyl)imide N-methyl-N-ethylpyrrolidin, [C7H16N]+N(CF3)2-that accounted for 93.4%.

19F-NMR (standard: CCl3F; solvent: CD3CN): -36,36

1H-NMR (standard: tetramethylsilane was; solvent: CD3CN): 1,34 TM (CH3); 2.17 m (2CH2); 2,27 C (CH3); 3,38 (CH2); 3,47 m (2CH2); J3n,n=7,3 Hz

Example 3

The solution 6,93 g (29,2 mmole) Rb+N(CF3)2-that was received from 2,05 g (29,2 mmole) RbF and 8.43 g (up 29.6 mmole) CF3SO2N(CF3)220 cm3dry acetonitrile was added at room temperature with stirring to a solution of 6.50 g (of 29.1 mmole) of tetrafluoroborate N-butylpyridinium 15 cm3dry acetonitrile. Reactio the ing the mixture was stirred at room temperature for 15 minutes, fallen in sediment RbBF4was filtered and washed with dry acetonitrile (2×5 cm3). The acetonitrile was removed under vacuum of 1.4 PA and the residue was dried for 2 hours at a temperature of 60-65°C. under reduced pressure, thus obtaining of 8.28 g butter-like substances.

The yield of bis(trifluoromethyl)imide N-butylpyridinium, [C9H14N]+N(CF3)2-$ 98.7%.

19F-NMR (standard: CCl3F; solvent: CD3CN): -36,23

1H-NMR (standard: tetramethylsilane was; solvent: CD3CN): 0,95 t (CH3); 1,38 m (CH2); 1.96 m (CH2); 4.59 (CH2); 8,06 m (2CH); 8,54 TT (CH); 8,92 DM 15 (2CH); J3n,n=7,3 Hz; J3n,n=7.5 Hz; Jn,n=7,9 Hz; Jn,n=1,8 Hz

Example 4

The solution of K+N(CF3)2-that was received from 1,90 g (32.7 mmole) spray dried potassium fluoride (KF) and 9,14 g (32,1 mmole) CF3SO2N(CF3)225 cm3dry dimethylformamide, was added at room temperature with stirring to a solution 6,28 g (31,7 mmole) of tetrafluoroborate 1-ethyl-3-methylimidazole 10 cm3dry dimethylformamide. The reaction mixture was stirred at room temperature for 15 minutes and successively cooled using an ice bath. Fallen in sediment KBF4hoteltravel is whether and washed with dry dimethylformamide (10 cm 3). The solvent was removed at 30-35°C. under vacuum of 1.3 PA. The liquid was separated from the precipitate, while receiving 7,8 g red-yellow butter-like substances.

The yield of bis(trifluoromethyl)imide 1-ethyl-3-methylimidazole, [C6H11N2]+N(CF3)2-that was 93.5% purity (in accordance with the measurement when using19F-NMR) 86,5%.

In order to improve the purity of the salt was dissolved in 10 cm3dry acetonitrile and treated with a solution of 1.35 g (5.7 mmole) Rb+N(CF3)2-8 cm3dry acetonitrile at room temperature. Fallen in sediment RbBF4was filtered and washed with dry acetonitrile (5 cm3). The acetonitrile was removed at a temperature of 30-35°C. under vacuum of 1.3 PA, while receiving 7,8 g bis(trifluoromethyl)imide 1-ethyl-3-methylimidazole, [C6H11N2]+N(CF3)2-having a purity of 98%.

19F-NMR (standard: CCl3F; solvent: CD3CN): -36,41

1H-NMR (standard: tetramethylsilane was; solvent: CD3CN): 1,45 t (CH3); 3,84 C (CH3); 4,18 to (CH2); 7,40 t (CH); 7,46 t (CH); 8,92 CL (CH); J3n,n=7,3 Hz; Jn,n=1.8 Hz

Example 5

The solution to 0.69 g (2.9 mmole) Rb+N(CF3)2-that was received from 0,303 g (2.9 mmole) f is orida RB RbF and 0,83 g (2.9 mmole) of CF 3SO2N(CF3)25 cm3dry acetonitrile, was added at a temperature of from -35 to -38°C with stirring to a solution of 0.71 g (2.9 mmole) of bromide N-ethylbenzothiazoline 10 cm3dry acetonitrile. The reaction mixture was stirred at a temperature of from -35 to -38°C for 15 minutes, precipitated in the sediment RbBr was sequentially filtered at this temperature and washed with dry acetonitrile (2×5 cm3). The residue amounted to 0.48 g of rubidium bromide (positive test with silver nitrate and the absence of signals in the spectrum of1H andl9F NMR). NMR spectroscopic investigation of a solution of acetonitrile at low temperature (-30°C) showed the formation of bis(trifluoromethyl)imide N-ethylbenzothiazoline.

19F-NMR (standard: CCl3F; solvent: CD3CN): - 39,15 C.

1. Salt saturated, partially or fully unsaturated heterocyclic cation containing anion bis(trifluoromethyl)imide, N(CF3)2-which have the General formula (1)

where the heterocyclic cations contain from 1 to 3 heteroatoms selected from nitrogen, sulfur or oxygen, and have a stable monocyclic or bicyclic structure containing from 3 to 8 members in the loop,
X is N, O or S,
n is an integer selected from 0, 1 or 2 such that X is saturated in the accordance with their valency, increased by 1,
And saturated, partially or fully unsaturated hydrocarbon chain containing from 4 to 8 members,
in which all carbon atoms except one, can be replaced by identical or different heteroatoms selected from N, O or S, where the carbon atoms of the hydrocarbon chain and present there heteroatoms are saturated substituents R2in accordance with their valences,
moreover, a and X together form a monocyclic or bicyclic structure containing 5 and/or 6 members in the loop,
R1, R2- -N, provided that no communication with positively charged heteroatom, alkyl with non-branched chain or branched, containing from 1 to 8 carbon atoms,
where R2and/or R1are in each case identical or different.

2. Salt according to claim 1, in which a represents a 4 - or 5-membered hydrocarbon chain.

3. Salt according to claim 1 or 2, in which a represents a hydrocarbon chain, in which zero, one or two carbon atoms are replaced by heteroatoms selected from N, O and S.

4. Salt according to any one of claims 1 to 3, in which
R1, R2independently of one another have the value
-N provided that not formed a connection with positively charged heteroatom,
alkyl with non-branched chain or branched, containing from 1 to 6 carbon atoms, h is particularly -CH3- 2H5, -n-C3H7, -CH(CH3)2, -n-C4H9, -N-C6H13.

5. Salt according to any one of claims 1 to 4, in which saturated, partially or fully unsaturated heterocyclic cation selected from the following groups:

where X Is N, O or S,
Y is in each case independently represents N, O, S, or s, where at least one Y=S,
n=1 for saturated X=O, S, or
2 for saturated X=N,
m=0 for saturated Y=O, S or unsaturated Y=N,
1 for saturated Y=N or Y=sp2-C
2 for Y=sp3C,
where the radicals R1, R2are as defined in claim 1.

6. Salt according to any one of claims 1 to 5, in which saturated, partially or fully unsaturated heterocyclic cation selected from the following groups:






7. Salt according to any one of claims 1 to 6, in which saturated, partially or fully unsaturated heterocyclic cation selected from the following groups:


8. Salt according to any one of claims 1 to 7, in which saturated, partially or fully unsaturated heterocyclic cation selected from the following groups:

9. The method of obtaining salt according to any one of claims 1 to 8, characterized in that the fluoride of the alkali metal General formula DF, where D is selected from the group of alkali metals, is subjected to reaction in a polar organic solvent with
RFSO2N(C 3)2or RFC(O)N(CF3)2
where RF=F or CpF2p+1where p=1-8,
and salt of the General formula (4)

where E-- F-, Cl-, Br-I-BF4-, ClO4-AsF6-, SbF6-, SbCl6-PF6-, RFSO3-, FSO3-, (RF)2R(O)-, (RF)R(O)2O-, RSO3-, POSO3-, 1/2SO32-CN-, SCN-, RFC(O)O-RC(O)O-, 2,4-dinitrophenol and 2,4,6-trinitrophenol, where RFrepresents a perfluorinated1-C8alkyl group or a perfluorinated aryl group, a R represents a C1-C6alkyl group or aryl group,
X is N, O or S,
n is an integer selected from 0, 1 or 2 such that X is saturated in accordance with its valency, increased by 1,
And saturated, partially or fully unsaturated hydrocarbon chain containing from 4 to 8 members,
in which all carbon atoms except one, can be replaced by identical or different heteroatoms selected from N, O and S,
where the carbon atoms of the hydrocarbon chain and present there heteroatoms are saturated substituents R2in accordance with avalanchestyle,
moreover, a and X together form a monocyclic or bicyclic structure containing 5 and/or 6 members in the loop,
R1, R2=-N provided that not formed a connection with positively charged heteroatom,
alkyl with non-branched chain or branched, containing from 1 to 8 carbon atoms,
where R2and/or R1in each case are identical or different.

10. The method according to claim 9, characterized in that the use of fluoride of an alkali metal, representing KF or RbF.

11. The method according to claim 9 or 10, characterized in that the reaction is carried out at temperatures from -40 to 80°C, in particular from 0 to 40°C.

12. The method according to any of PP-11, characterized in that the reaction is carried out in a polar organic solvent selected from the group comprising acetonitrile, dimethoxyethane, dimethylformamide and propionitrile.

13. The method according to any of PP-12, characterized in that the reaction is carried out as a reaction in the same tank.

14. The method according to any of PP-13, characterized in that the reaction for E-=F-carried out without addition of fluoride of an alkali metal DF.

15. The method according to any of PP-14, characterized in that the starting materials for the reaction using approximately equimolar ratio to each other.

16. The use of salts according to one of claims 1 to 8V as ionic liquid.

17. The use of salts according to one of claims 1 to 8 as a non-aqueous electrolyte.

18. The use of salts according to one of claims 1 to 8 as a reagent for the introduction of groups N(CF3)2.

19. The use of salts according to one of claims 1 to 8 as intermediate compounds for the synthesis of liquid-crystalline compounds or active ingredients, in particular, medicines or means for plant protection.



 

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1 ex, 1 tbl

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9 ex, 1 tbl

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