Method of producing onium salts with tetrafluoroborate anion, having low content of halides

FIELD: chemistry.

SUBSTANCE: invention relates to a new improved method of producing onium tetrafluoroborates through reaction of an onium halide with trialkyloxonium tetrafluoroborate, trialkylsulphonium tetrafluoroborate or triphenylcarbonium tetrafluoroborate, characterised by that the halide has formula (1) [XR4]+ Hal-, where X denotes N, P, Hal denotes Cl, Br or I and R in each case independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (2) [(R1R2N)-C(=SR7)(NR3R4)]+ Hal- (2), where Hal denotes Br or I R1-R7 each independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (3) [C(NR1R2)(NR3R4)(NR5R6)]+ Hal- (3), where Hal denotes CI, Br or I and R1-R6 each independently denotes a linear alkyl having 1-8 C atoms, or the halide has formula (4) [HetN]+ Hal- , where Hal denotes CI, Br or I and HetN+ denotes a heterocyclic cation selected from a group comprising imidazolium pyrrolidinium pyridinium where each of substitutes R1' - R4' independently denotes hydrogen, CN, linear or branched alkyl having 1-8 C atoms, dialkylamine containing alkyl groups having 1-4 C atoms but which is not attached to he heteroatom of the heterocyclic ring.

EFFECT: method enables to obtain products with low content of halides with high purity and high output.

5 cl, 12 ex

 

The invention concerns a method of obtaining niewyk salts with tetrafluoroborate anion by reaction viewage of the halide with hydronium tetrafluoroborate, sulfone tetrafluoroborate or triphenylcarbenium tetrafluoroborate.

A large number niewyk salts are ionic liquids. Thanks to its properties, ionic liquids are an effective alternative to traditional volatile organic solvents for organic synthesis in modern research. In addition, the use of ionic liquids as a new reaction medium could be a practical solution and removal of the solvents and the problems associated with re-processing catalysts (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 Flüssigkeiten - 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 or R. Hagiwara, Ya. Ito "Room temperature ionic liquids of alkylimidazolium cations and fluoroanions", J. Fluorine Chem., 105 (2000), 221-227).

Ionic liquids or liquid salts are ionic particles consisting of an organic cation and, typically, an inorganic anion. They do not contain any neutral molecules and usually their melting temperature below 373 K. However, the temperature of plaul the deposits may also be higher without limiting the use of these salts in all applications. Examples of organic cations, among others, are tetraalkylammonium, tetraalkylammonium, N-alkylpyridine, 1,3-dialkyl-imidazole or trialkylsilanes. Among a variety of suitable anions can be mentioned, for example, BF4-PF6-, SbF6-,

NO3-, CF3SO3-, (CF3SO2)2N-, S3-, CF3CO2-CH3CO2-or Al2CL7-.

Properties of ionic liquids, such as melting point, thermal and electrochemical stability or viscosity, determined by the choice of cations and anions. Ionic liquids are non-volatile materials and therefore can not be cleaned using standard cleaning methods, such as, for example, distillation, which is designed to most organic solvents.

Therefore, the methods of obtaining niewyk salts, in particular of ionic liquids with tetrafluoroborate anion, technology is critical to ensure that they can be synthesized with a low level of impurities directly by using reactions or ways of carrying out the reaction. The mixture, which prevails in the known ionic liquids, is ions of halogen the and. If the proportion of halogen ions such as chloride ions exceeds 1000 ppm (0,1%), the scope of the ionic liquid is reduced, particularly when applied to electrochemical processes.

Accordingly, the purpose of the present invention was to provide an alternative method of obtaining niewyk of tetrafluoroborates with low chloride content, which leads to the formation of products with high purity in good yield and is suitable for large-scale industrial production.

The goal can be achieved using a method in accordance with the invention. Accordingly, the present invention relates to a method for one of tetrafluoroborate using reaction viewage of the halide with trialkylamine tetrafluoroborate, sulfone tetrafluoroborate or triphenylcarbenium tetrafluoroborate.

The method in accordance with the invention represents an improvement over prior art synthetic methods for niewyk of tetrafluoroborate, which, as a rule, are 2-stage process, as described in .Wasserscheid and W.Keim, Angew. Chem. 112 (2000), 3926-3945. In the first stage, known methods of organic base, as a rule, amine, phosphine or a heterocyclic compound, alkylate using alkylhalogenide, and the resulting halide, in the second stage, turn in tetrafluoroborate by anionnogo the exchange.

In the second stage halide, such as 1-ethyl-3-methylimidazolium chloride or bromide, is introduced into reaction with the NaBF4in acetone according to the method of S. Park and R. J. Kazlauskas, J. Organic Chemistry, 66 (2001), 8395-8401, with the NaBF4in the water method R.Karmakar and A.Samanta, J. Phys. Chem. A 106 (2002), 6670-6675, with AgBF4or HBF4in water by the method of J. D. Holbrey and K. R. Seddon, J. Chem. Soc, Dalton Trans., (1999), 2133-2139, with NH4BF4in acetone according to the method J.Fuller et al, J.Electrochem. Soc, 144 (1997), 3881-3885, with HBF4in methanol according to the method of T. Nishida et al, J. of Fluorine Chem., 120 (2003), 135-141 or with NH4BF4with microwave irradiation method V.V. Namboodiri and R. S. Varma, TeTpahedron Lett., 43 (2002), 5381-5383.

All known methods have disadvantages, especially for large-scale industrial synthesis. For example, tetrafluoroborate silver is an expensive reagent. The reaction with the NaBF4, NH4BF4and HBF4in the water require a purification step, possibly using AgBF4or adsorbents. HBF4methanol is not commercially available and more expensive than the aqueous solution HBF4that is, in turn, commercially available reagent.

However, in the reaction in water HBF4halogen acid formed as a by-product, which cannot be removed from the final product by distillation, as the two of salt and two acids are in equilibrium in water. Received onevia tetrafluoroborate inevitably contain a few numbers of the ions of halogen, that is confirmed by the research N.M.M Mateus and coauthors, Green Chemistry, 5 (2003), 347-352.

To my surprise, was developed in a simple way. In response viewage of halide, for example chloride, bromide or iodide, with hydronium tetrafluoroborate, such as salt of Meerwein (Meerwein salt), sulfone tetrafluoroborate or triphenylcarbenium tetrafluoroborate, onevia tetrafluoroborate and alkylhalogenide or triphenylmethane and dialkyl esters or dialkyl sulfides, thus, are formed as by-products, which are either gases or volatile compounds, and can be removed from the reaction environment without a lot of engineering and technical measures. Some of these products are themselves valuable materials for organic syntheses.

The method in accordance with the invention allows to synthesize many tetrafluoroborate salts, in which different substituents, for example alkyl groups may be present on onieva cation, the so-called asymmetric connections. However, the new method can also be used for cleaning tetrafluoroborates that contain the anions chloride, bromide or iodide as contaminants. Thus, ionic liquids with tetrafluoroborate anions receive high quality without the use of expensive materials, such as tetrafluoroborate with the ribs, or without admixtures of silver cations.

Acceptable onevia halides in the case of reaction with trialkylamine tetrafluoroborate or triphenylcarbenium tetrafluoroborate represent phosphonium halides, Toroni halides, guanidinium halides or halides with a heterocyclic cation or in the case of reaction with trialkylsilanes tetrafluoroborate are ammonium halides, phosphonium halides, Toroni halides, guanidinium halides or halides with a heterocyclic cation, where the halides can be selected from the group of chlorides, bromides or iodides. The chlorides or bromides preferably used in the method in accordance with the invention. Toroni iodides are preferably used in the method in accordance with the invention for a class thiouronium salts.

Onevia halides are generally commercially available or can be obtained by methods of synthesis known from the literature, for example, described in standard works such as Houben-Weyl, Methods der organischen Chemie [Methods of organic chemistry], Georg-Thieme-Verlag, Stuttgart, or Richard .Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999. This can also be applied ways, known per se, which detail not mentioned in this description.

Onevia halides, as described above, or below, preferably used in the method in the affordable is accordance with the invention.

Phosphonium halides can be described, for example, formula (1)

in which

X represents N, R

Hal represents CL, Br or I and

R in each case independently of one another, is a

N, where all substituents R cannot simultaneously represent H,

linear or branched alkyl that has 1 to 20 With atoms

linear or branched alkenyl, which has 2-20 With atoms and one or

more double bonds,

linear or branched quinil, which has 2-20 With atoms and one or

more triple relations,

saturated, partially or fully unsaturated cycloalkyl, which has From 3-7 atoms which may be substituted by alkyl groups having 1-6 With atoms, where one or more R may be partially or fully substituted by F, but where all four or three R must not be fully substituted with F,

and where, in R, one or two non-adjacent carbon atoms which are not in the α - or ω-position may be replaced by atoms and/or groups of atoms selected from the group that includes-O-, -S-, -S(O)- or-SO2-.

However, excluded the compounds of formula (1), where all four or three substituent R is fully substituted by Halogens, such as Tris(trifluoromethyl)-methylammonium chloride, Tetra(trifluoromethyl)shumilkin) is chloride or Tetra(nonattorney)ammonium chloride, Tris(trifluoromethyl)methylphosphonic chloride, Tetra(trifluoromethyl)phosphonium chloride or Tetra(nonattorney)phosphonium chloride.

Toroni halides can be described, for example, using the formula (2)

and guanidine halides can be described, for example, using the formula (3)

where

Hal in the formula (2) represents Br or I, and in the formula (1) represents CL, Br or I, and

R1-R7each, independently of one another, is a

hydrogen or CN, where hydrogen is excluded for R7,

linear or branched alkyl that has 1 to 20 With atoms

linear or branched alkenyl, which has 2-20 With atoms and one or more double bonds,

linear or branched quinil, which has 2-20 With atoms and one or more triple relations,

saturated, partially or fully unsaturated cycloalkyl, which has From 3-7 atoms which may be substituted by alkyl groups having 1-6 With atoms, where one or more substituents R1-R7can be partially or fully substituted by F, but where all substituents on an N atom must not be fully substituted with F,

where the substituents R1-R7can be connected to one another in pairs using a simple or double bond,

and where, replace the s R 1- R6one or two non-adjacent carbon atoms which are not attached directly to the heteroatom and are not in the ω-position may be replaced by atoms and/or groups of atoms selected from the group that includes-O-, -S-, -S(O)- or-SO2-.

Halides with a heterocyclic cation can be described, for example, using the formula (4)

where Hal represents CL, Br or I and

HetN+represents a heterocyclic cation selected from the group that includes

where the substituents R1'-R4'each, independently of one another, represents hydrogen or CN,

linear or branched alkyl that has 1 to 20 With atoms

linear or branched alkenyl, which has 2-20 With atoms and one or more double bonds,

linear or branched quinil, which has 2-20 With atoms and one or more triple relations,

dialkylamino containing alkyl groups have 1-4 With the atom, but which is not attached to the heteroatom of the heterocycle,

saturated, partially or fully unsaturated cycloalkyl, which has From 3-7 atoms, which can the be replaced by alkyl groups, having 1-6 With atoms, or aryl-C1-C6-alkyl,

where the substituents R1'and R4'can be partially or fully substituted by F, but where R1'and R4'at the same time do not represent a CN or should not simultaneously be fully substituted by F,

where the substituents R2'and R3'can be partially or fully substituted by Halogens or partially by using the NO2or CN,

and where, in the substituents R1'- R4'one or two non-adjacent carbon atoms which are not attached directly to the heteroatom and are not in the ω-position may be replaced by atoms and/or groups of atoms selected from the group that includes-O-, -S-, -S(O)- or-SO2-.

For the purposes of the present invention fully unsaturated substituents also understand the importance of aromatic substituents.

In accordance with the invention, acceptable substituents R and R1-R7compounds of formulas (1)to(3), other than hydrogen, preferably represent: C1- - 20-, in particular C1- - 14-alkyl groups, and saturated or unsaturated, i.e. also aromatic, With3- - 7-cycloalkyl group which may be substituted with C1- - 6-alkyl groups, in particular phenyl. However, the substituents R and R1- R7also can be is substituted with additional functional groups, for example, using the CN, SO2R', SO2OR' or COOR'. R' represents a non-, partially or perforated C1- - 6-alkyl, C3- - 7-cycloalkyl, unsubstituted or substituted phenyl.

The substituents R in the compounds of formula (1) can be the same or different. Preferably, three of the substituent in the formula (1) are the same and one Deputy is different.

The substituent R represents particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.

Up to four substituents guanidinium cation can be connected in pairs in such a way that the formed mono-, bi - or polycyclic cations.

Examples of such cations guanidine are (but are not limited to them):

or,

where the substituents R1-R3and R6can take above or especially preferred meanings. Carbocycle or the heterocycles listed above guanidinium cations can be optionally replaced with C1- - 6-alkyl, C1 - - 6- alkenyl, NO2, F, Cl, Br, I, C1- - 6-alkoxy, SF3, SO2CH3, SO2CF3, COOR", SO2NR2, SO2X', SO3R', substituted or unsubstituted phenyl, where X' and R" are set above and below.

Up to four substituents Toranaga cation [(R1R2N)-C(=SR7)-(NR3R4)]+can also be connected in pairs in such a way that the formed mono-, bi - or polycyclic cations.

Examples of such cations are indicated below, but are not limited to them:

or,

where the substituents R1, R3and R7can take above or especially preferred meanings. Carbocycle or the heterocycles listed above guanidinium cations can be optionally replaced with C1- - 6-alkyl, C1- - 6-alkenyl, NO2, F, Cl, Br, I, C1- - 6-alkoxy, SCF3, SO2CH3, SO2CF3, COOR", SO2NR2, SO2X', SO3R', substituted or unsubstituted phenyl, where X' and R" are set above and below.

With1-C14is an alkyl group represents, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, furthermore also pentyl, 1-, 2 - or 3-IU is rbutil, 1,1-, 1,2 - or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl, optionally perfluorinated, such as deformity, trifluoromethyl, pentafluoroethyl, getattr-propyl or nonattorney.

Linear or branched alkenyl, which has 2-20 From the atom, where there may be many double bonds are present, for example, vinyl, allyl, 2 - or 3-butenyl, Isobutanol, second-butenyl, in addition, 4-pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, -C9H17, -C10H19up With20H39preferably allyl, 2 - or 3-butenyl, Isobutanol, second-butenyl, in addition, preferably 4-pentenyl, isopentenyl or hexenyl.

Linear or branched quinil, which has 2 to 20 C atoms, where there may be many ternary relationships, represents, for example, ethinyl, 1 - or 2-PROPYNYL, 2 - or 3-butynyl, in addition, 4-pentenyl, 3-pentenyl, hexenyl, heptenyl, octenyl, -C9H15, -C10H17up With20H37preferably ethinyl, 1 - or 2-PROPYNYL, 2 - or 3-butenyl, 4-pentenyl, 3-pentenyl or hexenyl.

Aryl-C1-C6-alkyl represents, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, fenilpentil or phenylhexa, where the phenyl ring, and also Allenova chain mouthbut partially or fully substituted, as described above, with F, particularly preferably benzyl or phenylpropyl. However, the phenyl ring or Allenova chain may also be substituted with additional functional groups, for example, using the CN, SO2R', SO2Or SIG' or COOR'. R' in this description takes the value specified above.

Substituted saturated or partially or fully unsaturated cycloalkyl groups which have From 3-7 atoms, thus, represent cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopent-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclo-hepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, each of which may also be substituted with1- - 6-alkyl groups, where cycloalkyl group or C1- - 6-alkyl-substituted cycloalkyl group in turn may be substituted by halogen atoms such as F, Cl, Br or I, in particular F or Cl, or NO2. However cycloalkyl groups can also be substituted with additional functional groups, for example, using the CN, SO2R', SO2OR' or COOR'. R' in this description takes the value specified above.

In the substituents R, R1-R6or R1'-R4'one or two non-adjacent atom is of Pereda, which is not attached to the α-position to the heteroatom or ω-position may be replaced by atoms and/or groups of atoms selected from the group that includes-O-, -S-, -S(O)- or-SO2-.

Without restricting generality, examples of the substituents R,R1-R6and R1'-R4'modified in this way include:

-Och3, -Och(CH3)2, -CH2Och3, -CH2-CH2-O-CH3- 2H4Och(CH3)2, -C2H4SC2H5,

-C2H4S(CH3)2, -S(O)CH3, -SO2CH3, -SO2With6H5, -SO2With3H7, -SO2CH(CH3)2,

-SO2CH2CF3, -CH2SO2CH3, -O-C4H8-O-C4H9, -CF3, -C2F5- 3F7, -C4F9, -CF2CF2H,

-CF2CHFCF3, -CF2SN(CF3)2, -C2F4N(C2F5)C2F5, -CHF2, -CH2CF3- 2F2H3- 3FN6,

-CH2With3F7, -CH2C(O)och3, -CH2With6H5or-S(O)6H5.

In R'3- - 7-pilooski represents, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

In R', substituted FeNi who represents phenyl, which is substituted with such as1- - 6-alkyl, C1- - 6alkenyl, NO2, F, Cl, Br, I, C1-C6-alkoxy, SF3, SO2CH3, SO2CF3, COOR", SO2X', SO2NR2or SO3R", where X' represents F, Cl or Br, and R" represents a non - or partially fluorinated C1- - 6-alkyl or C3- - 7-cycloalkyl as defined for R', for example, o-, m - or p-were, o-, m - or p-ethylphenyl, o-, m - or p-propylphenyl, o-, m - or p-isopropylphenyl, o-, m - or p-tert-butylphenyl, o-, m - or p-nitrophenyl, o-, m - or p-methoxyphenyl, o-, m - or p-ethoxyphenyl, o-, m-, p-(trifluoromethyl)phenyl, o-, m-, p-(trifter-methoxy)phenyl, o-, m-, p-(trifloromethyl)phenyl, o-, m - or p-fluoro-phenyl, o-, m - or p-chlorophenyl, o-, m - or p-bromophenyl, o-, m - or p-iodine-phenyl, particularly preferably 2,3-, 2,4-,

2,5-, 2,6-, 3,4 - or 3, 5dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-differenl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-

or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dibromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-acid, 5-fluoro-2-were, 3,4,5-trimethoxyphenyl or 2,4,5-trimetilfenil.

The substituents R1-R7each represents, independently of one another, preferably a linear or branched alkyl group which has 1-10 With atoms. The substituents R1and R2, R3and R4and R5and R6 in the compounds of formulas (2) and (3) can be the same or different.

R1-R7particularly preferably each represents, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, phenyl or cyclohexyl, more preferably methyl, ethyl, n-propyl, isopropyl or n-butyl.

In accordance with the invention, acceptable substituents R1'-R4'compounds of the formula (4), except hydrogen, are preferably CN, C1- - C20-especially With1- - 12-alkyl groups, and saturated or unsaturated, i.e. also aromatic, With3- - 7-cycloalkyl group which may be substituted with C1- - 6-alkyl groups, in particular phenyl or aryl-C1-C6is alkyl or diaminoalkyl, which has a1-C4-alkyl group, provided that they are not attached to the heteroatom. However, the substituents R1'-R4'can also be substituted with additional functional groups, for example, using the CN, SO2R', SO2OR' or COOR'. R' represents a non-, partially or perforated C1- - 6-alkyl, C3- - 7-cycloalkyl, unsubstituted or substituted phenyl.

The substituents R1and R4each represents, independently of one another, very special is about preferably CN, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl, phenylpropyl or benzyl. They are even more preferably CN, methyl, ethyl, n-butyl or hexyl. In pyrrolidinium, piperidinium or indolium connections two Deputy R1'and R4'are preferably different.

Deputy R2'or R3'represents in each case, independently of one another, in particular hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, tert-butyl, cyclohexyl, dimethylamino, diethylamino, methylethylamine, phenyl or benzyl. R2is particularly preferably dimethylamino, hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl. R2'and R3'represent even more preferably hydrogen, dimethylamino or methyl.

HetN+formula (4) is preferably

,

or

where the substituents R1'-R4'each, independently of one another, takes the value described above.

HetN+represents a particularly preferably of imidazole, pyrrolidine is whether pyridine, as described above, where the substituents R1'-R4'each, independently of one another, takes the value described above.

Used hydronium tetrafluoroborate having the formula [(alkyl)3O]+[BF4]-preferably represents a hydronium tetrafluoroborate having a linear or branched alkyl groups have 1-8 With atoms, which preferably have 1-4 atoms, which in each case are independent from one another. Preference is given to application of hydronium tetrafluoroborate, in which the alkyl groups are the same. You can also use tritely tetrafluoroborate, [(phenyl)3C]+[BF4]-.

Used sulfone tetrafluoroborate having the formula [(alkyl)3S]+[BF4]-preferably is sulfone tetrafluoroborate having a linear or branched alkyl groups have 1-8 With atoms, which preferably have 1-4 atoms, which in each case are independent from one another. Preference is given to using sulfone of tetrafluoroborate, in which the alkyl groups are the same.

Used hydronium tetrafluoroborate or sulfone tetrafluoroborate are generally commercially available or can be obtained by the methods of synthesis known to the literature, for example, as described in standard works such as Houben-Weyl, Methods der organischen Chemie [Methods of organic chemistry], Georg-Thieme-Verlag, Stuttgart, or Richard .Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999. This can also be applied ways, known per se, which detail not mentioned in this description.

Examples of hydronium tetrafluoroborate include trimethyloxonium tetrafluoroborate, triethyloxonium tetrafluoroborate (salt Meerwein), Tris(n-propyl)-hydronium tetrafluoroborate, dimethylethylamine tetrafluoroborate, diethyl-methyloctane tetrafluoroborate or Tris(ISO-propyl)hydronium tetrafluoroborate. Particular preference is given to the use of trimethyl - or triethyloxonium of tetrafluoroborate.

Examples of sulfone of tetrafluoroborate include trimethylsulfonium, triethyl-sulfone, dimethylethylamine, diethylmercury, DIPROPYLENE-sulfone, dipropylenetriamine, dibutylaminoethanol, di-sec-butyl-methylsulfone, dibutylaminoethanol tetrafluoroborate. Particular preference is given to using trimethylsulfonium and triethylsulfonium of tetrafluoroborate. The General scheme summarizes the method in accordance with the invention:

The substituents R, R1-R7and HetN+compounds of formulas (1)to(8) correspond to the values described above.

In the case of reaction with trialkylamine tetrafluoroborate or Triveni the-Carbonia-tetrafluoroborates the reaction is carried out in accordance with the invention at temperatures from 0 to 100°C, preferably at 20 to 50°, particularly preferably at room temperature. In the case of reaction with sulfonyl tetrafluoroborates the reaction is carried out in accordance with the invention at temperatures from 0 to 150°C, preferably at 20 to 100°C. Any solvent is not required. However, you can also use solvents such as dimethoxyethane, acetonitrile, dichloromethane, tetrahydrofuran, dimethyl sulfoxide, dioxane, propionitrile or mixtures of one with another.

The reaction is carried out with an excess or equimolar amount of the corresponding hydronium tetrafluoroborate, sulfone of tetrafluoroborate or triphenylcarbenium of tetrafluoroborate.

The described method is also suitable for the introduction of anions [(phenyl)4In]-PF6-, SbF6-or AsF6-in ionic liquids with onievymi cations by introducing into the reaction alkylammonium salts or alkylsulfonate salts with the corresponding anions with onievymi halides.

Even without additional comments it is clear that the specialist skilled in the art will be able to utilize the above description in its broadest scope. Therefore, the preferred embodiments and examples should be considered only as a disclosure of the invention, which absolutely does not limit it in any way. For professionals, verifizierung in the art, needless to say that the substituents in the compounds mentioned above and below, such as, for example, H, N, O, Cl, F, can be replaced by the corresponding isotopes.

NMR spectra were measured in solutions in datarecovery solvents at 20°C on a spectrometer Bruker Avance 300 with 5 mm1N/a BB broadband head with deuterium lock, if not specified in the examples. Measuring frequencies of different nuclei:1N: 300,13 MHz,11In: 96,92 MHz,19F: 282,41 MHz and31R: 121,49 MHz. Standards are specified separately for each spectrum or each set of data.

Examples

Example 1: Synthesis of 1-hexyl-3-methylimidazolium of tetrafluoroborate

2,09 g (br11.01 mmol) triethyloxonium of tetrafluoroborate add to of 2.21 g (10,90 mmol) of 1-hexyl-3-methylimidazolium chloride. The reaction mixture was stirred at room temperature for 30 minutes, and all volatile products are then removed within 30 minutes in a vacuum of 13.3 PA and 80°C. (oil bath temperature), resulting in 2,77 g of 1-hexyl-3-methylimidazolium of tetrafluoroborate in liquid form. The yield is almost quantitative.

1H NMR (standard: TMS; CD3CN), M. D.: 0,87 m (CH3); 1,29 m (SN2); 1,81 m (CH2); 3,82 s (CH3); 4,11 t (CH2); 7,34 d, d (CH); 7,38 (d, d (CH); of 8.47 br. s. (CH);3JN,N=7,1 Hz; JH,H=1,8 Hz.19F NMR (standard: CCl3F-inside the deposits; CD3CN), M. D.: -150,2 (BF4).

Example 2: Synthesis of 1-cyano-4-dimethylaminopyridine of tetrafluoroborate

2,95 g (15,53 mmol) triethyloxonium of tetrafluoroborate in 10 ml of dry dichloromethane was added to a suspension of 2.13 g (9,34 mmol) of 1-cyano-4-dimethylaminopyridinium bromide in 5 ml of dry dichloromethane. The reaction mixture was stirred at room temperature for 15 hours. All volatile products are removed within one hour in vacuo at 13.3 PA and room temperature. The residue is transferred in 10 ml of dry acetonitrile, and 1-cyano-4-dimethylaminopyridine tetrafluoroborate precipitated by adding 30 ml of ethyl acetate. Specified precipitate is filtered off and dried in vacuum at room temperature, which leads to obtain 1.40 g of solid substance. When partial distillation of the solvent still get 0,39, So output 1-cyano-4-dimethyl-aminopyridine of tetrafluoroborate is only 1,79 g, which corresponds to 81.6%.

1H NMR (standard: TMS; CD3CN), M. D. 3,32 s (2CH3); 6,98 d, m (2CH, A); 8,05 d, m (2CH);3JH(A)H(In)=8,1 Hz.

19F NMR (standard: CCL3F-internal; CD3CN), M. D.: - to 150.6 s (BF4).

13C NMR (standard: TMS; CD3CN), M. D.: 42.2 q, q [N(CH3)2]; 107,6 m (CN); 109,8 d, m (2CH); 141,5 d, m (2CH); 158,0 m (C)1JC,H=195 Hz;1JC,H=175 Hz;1JC,H=142 Hz;3JC,H3,3 Hz.

Raman spectrum: 2266,7 cm-1(CN). Elemental analysis of C8H10BF4N3(mol. weight 234,99): found: 40,78%, N Of 4.57%, N 18,10%calculated: 40,89%, N 4,29%, N 17,88%.

Example 3

Analogously to Example 1,

1 methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1 methylimidazole of tetrafluoroborate;

1 butylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1 butylimidazole of tetrafluoroborate;

1-ethyl-3-methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborate to obtain 1-ethyl-3-methylimidazole of tetrafluoroborate;

1-butyl-3-methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborate obtaining 1-butyl-3-methylimidazole of tetrafluoroborate;

1-methyl-3-intimidatory chloride is injected into reaction with diethyloxalate tetrafluoroborate to obtain 1-methyl-3-intimidatory of tetrafluoroborate;

3-methyl-1-octylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with 3-methyl-1-octylimidazolium of tetrafluoroborate;

1-decyl-3-methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborate obtaining 1-decyl-3-methylimidazolium of tetrafluoroborate;

1-dodecyl-3-methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-dodecyl-3-METI is imidazole of tetrafluoroborate;

3-methyl-1-tetradecylbenzene chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

3-methyl-1-tetradecylbenzene of tetrafluoroborate;

1-benzyl-3-methylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-benzyl-3-methylimidazole of tetrafluoroborate;

3-methyl-1-vinylimidazole chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

3-methyl-1-vinylimidazole of tetrafluoroborate;

1-ethyl-2,3-dimethylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-ethyl-2,3-dimethylimidazolium of tetrafluoroborate;

1-butyl-2,3-dimethylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-butyl-2,3-dimethylimidazolium of tetrafluoroborate;

1-hexyl-2,3-dimethylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-hexyl-2,3-dimethylimidazolium of tetrafluoroborate or

1-hexyldecyl-2,3-dimethylimidazolium chloride is injected into reaction with diethyloxalate tetrafluoroborates with receipt

1-hexyldecyl-2,3-dimethylimidazolium of tetrafluoroborate.

Example 4: Synthesis of 1-butylpyridinium of tetrafluoroborate

2,48 g (13,04 mmol) triethyloxonium of tetrafluoroborate added to the solution 2,77 g (12,82 mmol) 1-butylpyridinium bromide in 10 ml of dry dihl smetana. The reaction mixture was stirred at room temperature for 30 minutes. All volatile products are then removed within 30 minutes in a vacuum of 13.3 PA and 80°C. (oil bath temperature), resulting in 2,82 g 1 butylpyridinium of tetrafluoroborate in liquid form. The yield is almost quantitative.

1H NMR (standard: TMS; CD3CN), M. D.: 0,95 t (CH3); 1,37 m (CH2); 1,95 m (CH2); 4,54 t (CH2); 8,04 m (2CH); charged 8.52 t, t (CH); 8,73 d (2CH);3JH,H=7,3 Hz;3JH,H=7,6 Hz;3JH,H=7,9 Hz;3JH,H=5.7 Hz;4JH,H=1.2 Hz.19F NMR (standard: CCL3F-internal; CD3CN), M. D.: - 150,2 (BF4).

Similarly the way,

1 hexylpyridine chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

1 hexylpyridine of tetrafluoroborate;

1-butyl-4-methylpyridinium chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

1-butyl-4-methylpyridine of tetrafluoroborate;

1-butyl-3-methylpyridinium bromide is introduced into reaction with triethyloxonium tetrafluoroborate with receipt

1-butyl-3-methylpyridine of tetrafluoroborate or

1-butyl-3-ethylpyridinium bromide is introduced into reaction with triethyloxonium tetrafluoroborate with receipt

1-butyl-3-ethylpyridine of tetrafluoroborate.

Example 5: Synthesis of 1-ethyl-1-methylpyrrolidine of tetrafluoroborate

2,40 g (12,63 mmol) triethyloxonium of tetrafluoroborate added to a solution of 2.45 g (br12.62 mmol) 1-ethyl-1-methylpyrrolidinium bromide in 10 ml of dry dichloromethane. The reaction mixture was stirred at room temperature for 30 minutes. All volatile products are then removed within 30 minutes in a vacuum of 13.3 PA and 80°C. (oil bath temperature)that leads to the production of 2.53 g of 1-ethyl-1-methylpyrrolidine of tetrafluoroborate. The yield is almost quantitative.

1H NMR (standard: TMS; d3SP), M. D.: 1,31 t, m (CH3); 2,13 m (2CH2); 2,93 s (CH3); 3,32 q (CH2); 3,39 m (2CH2);3JH,H=7,3 Hz.

19F NMR (standard: CCL3F-internal; CD3CN), M. D.: - 150,4 s (BF4).

Similarly the way,

1-butyl-1-methylpyrrolidinium chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

1-butyl-1-methylpyrrolidine of tetrafluoroborate;

1-hexyl-1-methylpyrrolidinium chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

1-hexyl-1-methylpyrrolidine of tetrafluoroborate;

1-methyl-1-octylpyrimidine chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

1-methyl-1-octylpyrimidine of tetrafluoroborate;

trioxymethylene chloride is injected into reaction with triethyloxonium tetrafluoroborate with receipt

trioxymethylene is Travelport.

Example 6: Synthesis of N,N,N',N'-tetramethyl-N"-ethylguanidine of tetrafluoroborate

3,20 g (equal to 16.83 mmol) triethyloxonium of tetrafluoroborate added to a solution of 3.73 g (16,64 mmol) N,N,N',N'-tetramethyl-N"-ethylguanidine bromide in 10 ml of dry dichloromethane. The reaction mixture was stirred at room temperature for 30 minutes. All volatile products are then removed within 30 minutes in a vacuum of 13.3 PA and 80°C. (oil bath temperature), which leads to the obtaining of 3.84 g of N,N,N',N'-tetramethyl-N"-ethyl-guanidine of tetrafluoroborate.

The yield is almost quantitative.

1H NMR (standard: TMS; CD3CN), M. D.: 1,11 t (CH3); 2,86 br. s; 2,87 br. s; 2,91 s (SN3); 3,20 m (CH2); 6,17 br. s (NH);3JH,H=7,1 Hz.

19F NMR (standard: CCl3F - internal; CD3SP), M. D.: - 150,4 s (BF4).

Example 7: Synthesis tetrabutylphosphonium of tetrafluoroborate

2.14 g (11,27 mmol) triethyloxonium of tetrafluoroborate added to the solution 3,81 g (11,23 mmol) tetrabutylphosphonium bromide in 10 ml of dry dichloromethane. The reaction mixture was stirred at room temperature for 30 minutes. All volatile products are then removed within 30 minutes in a vacuum of 13.3 PA and 80°C. (oil bath temperature), which leads to obtain 3.88 g tetrabutylphosphonium of tetrafluoroborate. The yield is almost quantitative./p>

1H NMR (standard: TMS; CD3CN), M. D.: 0,94 t (CH3); 1,47 m (2CH2); 2,05 m (CH2);3JH,H=7,1 Hz.

19F NMR (standard: CCL3F - internal; CD3JV), ppm: - 150,4 s (BF4).

Example 8: Synthesis of 1-butyl-3-methylimidazole of tetrafluoroborate

7,06 g (to 34.3 mmol) triethylsulfonium of tetrafluoroborate, (C2H5)3S+BF4-added to 5,98 g (a 34.2 mmol) of solid 1-butyl-3-methylimidazolium chloride. The reaction mixture is stirred for 4 weeks at 60-70°C (oil bath temperature) and in the atmosphere of inert gas (nitrogen). All volatile products are pumped for 3 hours at a bath temperature of 70°C and at a pressure of 13.3 PA, resulting in 7,74 g of liquid. Output 1-butyl-3-methylimidazole of tetrafluoroborate almost quantitative. The product received is examined using NMR spectroscopy.

1H NMR (standard: TMS; solvent: CD3CN), M. D.: 0,91 t (CH3); 1,29 m (CH2); 1,79 m (CH2); 3,82 s (CH3); 4,13 t (CH2); of 7.36 (d,d (CH); 7,39 d, d (CH); 8,61 br. s. (CH);CJH,H=7,2 Hz; JH,H=l,5 Hz.

19F NMR (standard: CCL3F - internal; solvent: CD3CN), M. D.: - to 150.1 (BF4).

Example 9: Synthesis of 1-hexyl-3-methylimidazolium of tetrafluoroborate

5,38 g (26,1 mmol) triethylsulfonium of tetrafluoroborate, C 2H5)3S+BF4-added to 5,28 g (26 mmol) of liquid 1-hexyl-3-methylimidazolium chloride. The reaction mixture is stirred for 3 weeks at 60-70°C (oil bath temperature) and in the atmosphere of inert gas (nitrogen). All volatile products are pumped for 3 hours at a bath temperature of 70°C and at a pressure of 13.3 PA, which leads to obtain 6.6 g of a liquid. Output 1-hexyl-3-methylimidazolium of tetrafluoroborate almost quantitative. The product received is examined using NMR spectroscopy.

1H NMR (standard: TMS; solvent: CD3CN), M. D.: 0,87 m (CH3); 1,29 m (3CH2); 1,81 m (CH2); 3,82 s (CH3); 4,11 t (CH2); 7,34 d, d (CH); 7,37 d,d (CH); 8,50 br. s. (SN);3JH,H=7,1 Hz; JH,H=1.5 Hz.

19F NMR (standard: CCL3F - internal; solvent: CD3CN), M. D.: - 150,2 (BF4).

Example 10: Synthesis of 1-butylpyridinium of tetrafluoroborate

The mixture 4,82 g (of 22.3 mmol) N-butylpyridinium bromide and to 4.62 g (of 22.4 mmol) triethylsulfonium of tetrafluoroborate, (C2H5)3S+BF4-injected into the reaction for 24 hours at 85-90°C (oil bath temperature) under dynamic pressure of 7 PA. After cooling to room temperature gain equal to 4.97 g of oil. Output N-butylpyridinium of tetrafluoroborate almost quantitative. The product received is examined with OSU NMR spectroscopy.

1H NMR (standard: TMS; solvent: CD3SP), M. D.: 0,93 t (CH3); 1,35 m (CH2); 1,95 m (CH2); 4,58 t (CH2); 8,05 m (2CH); charged 8.52 t, t (CH); 8,82 d (2CH);3JH,H=7,6 Hz;3JH,H=7,2 Hz;3JH,H=7,9 Hz;4JH,H=1,4 Hz.

19F NMR (standard: CCl3F - internal; solvent: CD3CN), M. D.: - to 150.1 (BF4).

Example 11: Synthesis of S-ethyl-N,N,N',N'-tetramethylthiourea of tetrafluoroborate

A mixture of 1.07 g (3,71 mmol) of S-ethyl-N,N,N',N'-tetramethylthiourea iodide and 0.77 g (3,74 mmol) triethylsulfonium of tetrafluoroborate, (C2H5)3S+BF4-injected into the reaction for 20 hours at 85-90°C (oil bath temperature) under dynamic pressure of 7 PA. After cooling to room temperature gain of 0.92 g of solid substance. The S-ethyl-N,N,N',N'-tetramethylthiourea of tetrafluoroborate almost quantitative. Melting point equal 72-76°C. the resulting product are examined using NMR spectroscopy.

1H NMR (standard: TMS; solvent: CD3CN), M. D.: 1,31 t (CH3); 3,01 q (CH2); 3,23 s(4CH3);3JH,H=7,4 Hz.

19F NMR (standard: CCl3F - internal; solvent: CD3SP), M. D.: - 150,5 (BF4).

Example 12: Synthesis of 1-hexyl-3-methylimidazolium of tetrafluoroborate

0,912 g (was 2.76 mmol) triphenylcarbenium those who of reverberate, (C6H5)3C+BF4-and 5 cm3benzene is added to 0.56 g (was 2.76 mmol) of 1-hexyl-3-methyl-imidazole chloride. The reaction mixture was stirred at room temperature for 30 minutes. Top (benzene) phase is separated, and the product is washed three times with 10 ml of benzene. The residue is dried in vacuo at 13.3 PA at a bath temperature of 100°C, which leads to obtain 0.7 g of a liquid. Output 1-hexyl-3-methylimidazolium of tetrafluoroborate almost quantitative. The product received is examined using NMR spectroscopy.

1H NMR (standard: TMS; solvent: CD3SP), M. D. 0,89 m (CH3); 1,31 m (3CH2); 1,82 m (CH2); 3,84 s (CH3); 4,11 m (CH2); of 7.36 (d,d (CH); 7,39 d,d (CH); 8,50 br. s. (CH);3JH,H=7,2 Hz; JH,H=1,7 Hz.

19F NMR (standard: CCL3F-internal; solvent: CD3SP), M. D.: - 150,2 (BF4).

1. The method of obtaining niewyk of tetrafluoroborate by introducing into the reaction viewage of the halide with trialkylamine tetrafluoroborate, trialkylsilanes tetrafluoroborate or triphenylcarbenium tetrafluoroborate, characterized in that the halide conforms to the formula (1)
,
where X represents N, P,
Hal represents CL, Br or I and
R in each case independently of one another, represents a linear alkyl that has 1 to 8 With atoms, or galag the NID corresponds to the formula (2)

where Hal represents Br or I and
R1-R7each, independently of one another, represents a linear alkyl that has 1 to 8 With atoms, or
the halide conforms to the formula (3)

where Hal represents CL, Br or I and
R1-R6each, independently of one another, represents a linear alkyl that has 1 to 8 With atoms, or
the halide conforms to the formula (4)

where Hal represents CL, Br or I and
HetN+represents a heterocyclic cation selected from the group that includes

where the substituents R1'-R4'each, independently of one another represent hydrogen, CN, linear or branched alkyl that has 1 to 8 With atoms, dialkylamino containing alkyl groups have 1-4 With the atom, but which is not attached to the heteroatom of the heterocycle.

2. The method according to claim 1, characterized in that the halide in the case of reaction with trialkylamine tetrafluoroborate or triphenylcarbenium tetrafluoroborate is an ammonium halide, phosphonium halide, guanidine halide or halide with a heterocyclic cation, or in the case of reaction with trialkylsilanes tetrafluoroborate is Toroni halide or halogenide with a heterocyclic cation.

3. The method according to claim 1 or 2, characterized in that the use of the hydronium tetrafluoroborate.

4. The method according to claim 1 or 2, characterized in that in the case of reaction with trialkylamine tetrafluoroborate or triphenylcarbenium tetrafluoroborate the reaction is carried out at a temperature from room temperature up to 100°C, and in the case of reaction with sulfonyl tetrafluoroborates the reaction is carried out at a temperature of from 60 to 150°C.

5. Application of the method according to any one of claims 1 to 4 for cleaning niewyk of tetrafluoroborates that dirty onievymi halides.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to ionic liquid used in electrical energy accumulation devices and as a solvent which contains a cation of general formula where X1, X2 and X3 denote N, O, S or C; R1-R11, X1, R1, R2 and R3, X2, R6, R7 and R8, X3, R9, R10 and R11 can form ring structures; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, PF6-, [RfPF5]-, BF4-, [RfBF3]-, SO42-, HSO4-, NO3- I-, bis(oxalate)borate; R, R1-R11 are selected from hydrogehn, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl, halogen, CN- or NO2-; the carbon in R and R1-R11 can be substituted with O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N= -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R4 -P(O)R'-O-, -O-P(O)R'-O- and -P(R')2=N-; where R' denotes alkyl, fluoroalkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl; Rf denotes a fluorine-containing substitute.

EFFECT: obtaining novel ionic liquids which are stable in liquid state in a wide temperature range.

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to ionic liquid used in electrical energy accumulation devices and as a solvent which contains a cation of general formula where X1, X2 and X3 denote N, O, S or C; R1-R11, X1, R1, R2 and R3, X2, R6, R7 and R8, X3, R9, R10 and R11 can form ring structures; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [R2P(O)O]-, [RP(O)O2]2-, [(RO)2P(O)O]-, [(RO)P(O)O2]2-, [(RO)(R)P(O)O]-, [Rf2P(O)O]-, [RfP(O)O2]2-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, PF6-, [RfPF5]-, BF4-, [RfBF3]-, SO42-, HSO4-, NO3- I-, bis(oxalate)borate; R, R1-R11 are selected from hydrogehn, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl, halogen, CN- or NO2-; the carbon in R and R1-R11 can be substituted with O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N= -N=N-, -NH-, -NR'-, -N(R')2-, -PR'-, -P(O)R4 -P(O)R'-O-, -O-P(O)R'-O- and -P(R')2=N-; where R' denotes alkyl, fluoroalkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl or heterocyclyl; Rf denotes a fluorine-containing substitute.

EFFECT: obtaining novel ionic liquids which are stable in liquid state in a wide temperature range.

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to ionic liquids based on a cation of formula (1): where substituting groups R1-R9 are selected from hydrogen, alkyl; any carbon atom in R1-R9 can be substituted with a -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2- or -SO3- group; X is S, O or C; R8 and R9 exist only when X is carbon; the anion is selected from [RSO3]-, [RfSO3]-, [(RfSO2)2N]-, [(FSO2)3C]-, [RCH2OSO3]-, [RC(O)O]-, [RfC(O)O]-, [CCl3C(O)O]-, [(CN)3C]-, [(CN)2CR]-, [(RO(O)C)2CR]-, [B(OR)4]-, [N(CF3)2]-, [N(CN)2]-, [AlCl4]-, PF6-, BF4-, SO42-, HSO4-, NO3-; where R is hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, Rf is a fluorine-containing substituting group.

EFFECT: obtaining new ionic liquids with improved electrochemical properties.

15 cl, 18 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: claimed invention relates to copolymers of diallylaminophosphonium salts with sulphur dioxide demonstrating antimicrobial activity with respect to a number of bacteria, as well as to yeast-like fungi and spores, and can be applied as antiseptic and disinfecting means. Claimed copolymers of diallylaminophosphonium salts with sulphur dioxide aree characterised by general formula where A=Cl- or BF4-. They are soluble in methanol, DMSO, DMFA or if A=Cl- are soluble in water. They are obtained by copolymerisation of equimolar amounts of sulphur dioxide and diallylaminophosphonium salt, selected from tris(diethylamino)diallylaminophosphonium chloride or tris(diethylamino)diallylaminophosphonium tetrafluoroborate.

EFFECT: obtaining novel efficient and low-toxic compounds which do not cause corrosion of processed metals.

2 cl, 3 tbl, 4 ex

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

FIELD: chemistry.

SUBSTANCE: invention refers to organic chemistry, namely, to method of production of functionally substituted fullerenes to be applied as complexing agents, sorbents, biologically active compounds, as well as for production of new materials with specified electronic, magnetic and optical properties. Substance of the method consists in production of 2,3-fullero[60]-7-phenyl-7-phosphabicycklo[2.2.1]heptanes of formula (I) as resulted from reaction of fullerene C60 and phenylphospholane with catalyst Cp2TiCl2 added in toluol medium at temperature 140-160°C within 4-8 hours.

EFFECT: new method of selective production of functionally substituted fullerenes with end product yield 46-68%.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: in phosphazene, applied on carrier, catalyst for cyclic monomer polymerisation or for substituent substitution in compound or for carrying out reaction with formation of carbon-carbon bond, carrier is insoluble in used solvent and has group, which is able to form bond with group described with general formula (1) where n is integer in interval from 1 to 8 and represents number of phosphazene cations, Zn- is anion of compound, containing atoms of active hydrogen in form obtained as result of release of n protons from compound, which contains atoms of active hydrogen, in which there are , at most, 8 atoms of active hydrogen; each of a, b, c and d represents positive integer equal 3 or less; R represents similar or different hydrocarbon groups, containing from 1 to 10 carbon atoms, and two R, located on each common nitrogen atom, can be bound with each other with formation of ring structure; R1 represents hydrogen atom or hydrocarbon group, containing from 1 to 10 carbon atoms; D represents direct bond or divalent group able to bind N with carrier. Described are phosphazene compound and phosphazene salts and methods of cyclic monomer polymerisation, substitution of substituent in compound and carrying out of reaction with formation of carbon-carbon bond using applied on carrier catalyst. According to invention method polymerisation of cyclic monomers, substitution of substituents, reactions with formation of carbon-carbon bond, etc. can be carried out with extremely high efficiency.

EFFECT: increase of efficiency of carrying out different organic reactions and absence of activity decrease even after removal and re-use of catalyst, economic benefit.

10 cl

FIELD: biology, medicine, organic chemistry.

SUBSTANCE: invention proposes compound of the general formula (I): wherein A means effector group; L means a linker link; B represents Skulachev-ion Sk or charged hydrophobic peptide. Compound can be used in preparing a pharmaceutical composition for target (directed) delivery of active substances in mitochondria carried out by electrochemical potential of hydrogen ions into mitochondria. Also, invention can be useful in treatment of diseases and states associated with disturbance of normal function of mitochondria, in particular, diseases associated with increased formation of free radicals and active forms of oxygen. The claimed invention owing to directed accumulation of biologically active substance in mitochondria provides enhancing the effectiveness of substance, to decrease total dose, probability and strength of adverse effects.

EFFECT: improved and valuable properties of method and pharmaceutical composition.

26 cl, 14 dwg, 16 ex

FIELD: reduction of ferric sulfide deposits in pipe lines.

SUBSTANCE: proposed method consists in bringing the inner surfaces of pipe in contact with composition prepared from aqueous solution containing the compounds given in formula (I): , where X is anion whose valence "n" is selected from definite group and at least one amine selected from group including alkyl amines, dialkyl amines, alkylen diamines, cycloalkyl amines or their conjugates with acids. According to another version, use is made of composition containing tris(hydroxymnethyl) phosphine, at least one amine or its conjugate with acid and solvent. In presence of composition, fast complexation takes place; as a result, ferric sulfide deposits are dissolved and are removed from pipe.

EFFECT: possibility of using safe, available and inexpensive materials ensuring deposition of polymers.

72 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing complexes of 2-isopropoxy-2-methylvinyl trichlorophosphonium hexachlorometals of the general formula: [(I-PrO-C(CH3)=CHP+Cl3)nMCln-6] wherein M means Sn; n = 2; M means Sb or Bi; n = 3. Method involves interaction of diisopropyl ester with phosphorus pentachloride in the inert solvent medium followed by treatment of formed compound with tin, antimony of bismuth dichloride. Before treatment of formed compound with the corresponding anhydrous metal dichloride nitromethane as a polar solvent is added to its in the amount 1.1-1.25 mole per 1 mole of phosphorus pentachloride, and mixture is heated to temperature above 55°C up to formation of the end product. Method provides increasing yield of the end product.

EFFECT: improved preparing method.

3 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: there is described a compound of formula I: or its pharmaceutically acceptable salt, where R2 represents (CR3R4)n-NR5R6 and m, p, q, Ar, R1, R3, R4, R5 and R6 are those as specified in the patent claim and defined as selective 5-NT6 and/or 5-NT2A antagonists. There is also described a pharmaceutical composition containing this compound, and application thereof in preparing drugs for treating diseased conditions of central nervous system chosen from psychoses, schizophrenia, manic depressions, neural disorders, memory impairment, attention deficient syndrome, Parkinson's disease, amyotrophic lateral sclerosis, Alzheimer's disease, malnutrition and Huntington's disease.

EFFECT: preparation of the compounds which can find application in treatment of a diseased condition of central nervous system.

27 cl, 1 tbl, 29 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to compounds of formula (I) and their pharmaceutically acceptable salts and esters. The disclosed compounds have LXR-alpha and/or LXR-beta agonist properties. In formula (I) R1 is hydrogen, halogen; R2 is lower alkyl, flouro-lower alkyl; R3 is hydrogen, phenyl; R4 is hydrogen, hydroxy; R5 is hydrogen; phenyl; R6 is phenyl, a 5-6-member heteroaryl with one or two heteroatoms selected from nitrogen and sulphur, a 9-member bicyclic heteroaryl with a sulphur atom as a heteroatom, which can be optionally substituted with a halogen, or R6 is , R7 is a lower alkyl; R8 is phenyl which is optionally substituted with one substitute selected from a group consisting of halogen, fluoro-lower alkyl, R9-O-C(O)-, R10R11NC(O)-, phenyl-lower alkoxy; R9, R10, R11 independently represent hydrogen or lower alkyl; L is a single bond, lower alkylene or lower alkenylene; m assumes values from 0 to 3; n is equal to 0 or 1.

EFFECT: obtaining a new compound and a pharmaceutical composition which contains the disclosed compound as an active ingredient for therapeutic and/or preventive treatment of diseases.

23 cl, 47 ex

FIELD: chemistry.

SUBSTANCE: invention refers to synthesis of [18F]fluororganic compounds ensured by reaction of [18F]fluoride and relevant halogenide or sulphonate with alcoholic vehicle of formula 1 where R1, R2 and R3 represent hydrogen atom or C1-C18 alkyl.

EFFECT: possibility for mild process with low reaction time and high yield.

21 cl, 2 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to new displaced heterocyclic derivatives that can be used in treatment of diabetes and to reduce the content of cholesterol. In formula m is 1; n is 1; Q is C; A is -(CH2)x2-0-(CH2)x3-, where x2 varies from 1 to 3 and x3 is 0; B is a bond or it is (CH2)x4, where x4 varies from 1 to 2; X represents CH or N; X2, X3, X4, X5, X6 represent C, N, O; provided that one from X2 X3 X4 X5 and X6 represents N; and at least one of X2, X3, X4, X5, and X6 represents C; R1 represents H or C1-C6alkyl; R2 is H; R2a, R2b and R2c can be equal or different and selected from H, C1-C6alkyl, C1-C6alkoxy, halogen or thyano; R3 is selected from phenyloxycarbonile, C1-C6alkyloxycarbonile, phenylcarbinol, phenyl, alkoxy; Y represents CO2R4 (where R4 represents H or C1-C6alkyl); (CH2)m can be not necessarily displaced by 1 substitute.

EFFECT: produced are pharmaceutical composition for treatment of diabetes and to reduce the content of cholesterol.

13 cl, 2 tbl, 22 dwg, 88 ex

FIELD: chemistry of organophosphorus compounds, chemical technology.

SUBSTANCE: invention describes a method for synthesis of monohydroperfluoroalkanes, bis-(perfluoroalkyl)phosphinates and perfluoroalkylphosphonates. Method involves treatment of at least one perfluoroalkylphosphorane with at least one base wherein base(s) are chosen from group consisting of alkali-earth metal hydroxides, metalloorganic compound in useful solvent or at least one organic base and an acid in useful reaction medium. Also, invention describes novel perfluoroalkylphosphonates and bis-(perfluoroalkyl)phosphinates, using novel perfluoroalkylphosphonates and bis-(perfluoroalyl)phosphinates as ionic liquids, catalysts of phase transfer or surfactants.

EFFECT: improved method of synthesis.

18 cl, 19 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to using phenylethenyl- or phenylethynyl-derivatives as antagonists of glutamates receptors. Invention describes using compound of the general formula (I):

wherein each among R1, R2, R3, R4 and R5 means independently of one another hydrogen atom, (C1-C6)-alkyl, -(CH2)n-halogen, (C1-C6)-alkoxy-group, -(CH2)n-NRR', -(CH2)n-N(R)-C(O)-C1-C6)-alkyl, phenyl or pyrrolyl that can be unsubstituted or substituted with one or more (C1-C6)-alkyl; each among R, R' and R'' means independently of one another hydrogen atom or (C1-C6)-alkyl; A means -CH=CH- or C≡C; B means ,, , , or wherein R6 means hydrogen atom, (C1-C)-alkyl, -(CH2)n-C(O)OR, or halogen atom; R7 means hydrogen atom, (C1-C6)-alkyl, -(CH2)n-C(O)OR', halogen atom, nitro-group or oxodiazolyl group that can be unsubstituted or substituted with (C1-C6)-alkyl or cycloalkyl; R8 means hydrogen atom, (C1-C6)-alkyl, -(CH2)n-OH, -(CH2)n-C(O)OR'' or phenyl; R9 means (C1-C6)-alkyl; R10 and R11 mean hydrogen atom; R12 means -(CH2)n-N(R)-C(O)-(C1-C6)-alkyl; R13 means hydrogen atom; each R14, R15, R16 and R17 independently of one another means hydrogen atom or (C1-C6)-alkoxy-group; each R18, R19 and R20 independently of one another means hydrogen atom; R21 means hydrogen atom or (C1-C6)-alkyl; R22 means hydrogen atom, (C1-C6)-alkyl or (C1-C6)-alkyl comprising one or more substitutes chosen from groups hydroxy- or halogen atom; R23 means hydrogen atom, (C1-C6)-alkanoyl or nitro-group; each among R24, R25 and R26 independently of one another means hydrogen atom or (C1-C6)-alkyl; n = 0, 1, 2, 3, 4, 5 or 6; X means -O- or -S-; Y means -CH= or -N=, and its pharmaceutically acceptable salts used in preparing medicinal agents designates for treatment or prophylaxis of disorders mediated by mGluR5-receptors. Also, invention describes compounds of the formula (I-A), compound of the formula (I-B-1) given in the invention description, and a medicinal agent used in treatment or prophylaxis of disorders mediated by mGluR5-receptors.

EFFECT: valuable medicinal properties of compounds.

44 cl, 1 tbl, 44 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to derivatives of adamantine, in particular, to a new method for preparing adamant-1-yl-containing azoles of the general formula I-VIII: wherein R1 means ; R2 means ; R3 means ; R4 means ; R5 means ; R6 means ; R7 means , and R8 means . Indicated derivatives of adamantine are semifinished products used in synthesis of biologically active substances. Proposed method for preparing these compounds involves using a new method for synthesis of adamant-1-yl-containing azoles that includes the addition reaction of azoles: 2-methylimidazole, 3(5)-methylpyrazole and 4-methylpyrazole, 3,4-dinitropyrazole, 1,2,4-triazole, 3-methylpyrazole, 3-nitro-1,2,4-triazole and 5-methyltetrazole to 1,3-dehydroadamantane in the mole ratio of 1,3-dehydroadamantane to azole = 1:1 in diethyl ether medium at temperature 100°C for 4-5 h.

EFFECT: improved preparing method.

8 ex

The invention relates to imidazole derivative of General formula I, where n=0 or 1, R1is hydrogen, alkyl, R2is hydrogen or R2and R3form a double bond, R3is hydrogen, alkyl, R4is hydrogen, alkyl, hydroxy-group, alkoxy, R5is hydrogen or alkyl, or R4and R5form a carboxyl group, R6, R7, R8is hydrogen, alkyl, hydroxy-group, alkoxy, hydroxyalkyl, halogen, X-CHR9-(CHR10)m-, m = 0 or 1, R9and R10is hydrogen or alkyl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to novel amide derivatives of general formula [1] in any of versions (A) or (B), or its pharmaceutically acceptable salt, which possess properties of tyrosinkinase BCR-ABL inhibitor. Amide derivative of general formula [1] represents compound: , where according to Version (A) R1 represents any of the following groups (1)-(3): (1) -) -CH2-R11 [R11 represents saturated 4-6 member nitrogen-containing heterocyclic group, optionally containing additional nitrogen atom; saturated 5-6-member nitrogen-containing heterocyclic group, optionally containing additional nitrogen atom, which is substituted by group selected from group, consisting of oxo, -CH2-R111 (R111 represents saturated 5-member nitrogen-containing heterocyclic group), saturated 5-member nitrogen-containing heterocyclic group, aminomethyl, monoalkylaminomethyl, dialkylaminomethyl and (5-methyl-2-oxo-1,3-Dioxol-4-yl)methyl, and in addition, can be substituted by 1 or 2 similar or different substituents, selected from group, consisting of (C1-C4)alkyl, (C1-C4 alkoxycarbonyl, halogen, halogen(C1-C4)alkyl, hydroxy(C1-C4)alkyl, amino, carbamoyl], (2) -O-R12 [R12 represents saturated 4-6-member nitrogen-containing heterocyclic group]; and (3) - CH=R13 [R13 represents saturated 4-6-member nitrogen-containing heterocyclic group, which can contain additional nitrogen atom, and which can be substituted by 1-3 similar or different substituents, selected from group, consisting of oxo, (C1-C4)alkyl]; R2 represents (C1-C4)alkyl, halogen, halogen(C1-C4)alkyl, hydroxy(C1-C4)alkyl, (C1-C4)alkoxy and carbamoyl; R3 represents hydrogen, halogen; Het1 represents any of groups with the following chemical formulae [4] and [6]: [4] [6] [19] [10] Het2 represents pyridyl or pyrimidinyl. According to Version (B) R1 represents -CH2-R14 [R14 represents saturated 4-6-member nitrogen-containing heterocyclic group, optionally containing additional nitrogen atom; saturated 5-6-member nitrogen-containing heterocyclic group, which can be substituted by 1-3 similar groups, selected from (C1-C4)alkyl] R2 represents (C1-C4)alkyl, halogen, halogen(C1-C4)alkyl, hydroxy(C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkoxy (C1-C4)alkyl, (C1-C4)alkoxycarbonyl, (C1-C4)acyl, amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, nitro, carbamoyl, mono(C1-C4)alkylcarbamoyl, di(C1-C4)alkylcarbamoyl or cyano; R3 represents hydrogen or halogen; Het1 represents any of groups with the following chemical formulas [9] and [10], Het2 represents pyridyl.

EFFECT: invention can be applied for treatment of chronic myeloleukosis, acute lymphoblastic leukosis and acute myeloblastic leukosis.

6 cl, 89 ex, 3 tbl

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