Ionic liquid containing phosphonium cation with p-n bond, and method of producing said liquid

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

 

The technical field to which the invention relates.

The present invention relates to ionic liquid, which is in a liquid state in a wide temperature range and has excellent electrochemical stability; to a method for producing the ionic liquid and its applications, including devices for accumulating electric energy, lithium batteries, capacitors, electric double layer (edlcs), solar cells based on sensitized inks, fuel cells, solvents for the implementation of the reactions and the like.

The level of technology

In many publications have already reported about ionic liquids, which have a relatively low viscosity and melting point and represent a system based on ion imidazole. However, ionic liquids have already been reported, lack of stability due to the lower stability and narrow electrochemical window, however, many ionic liquids have such a disadvantage as difficult to use as the electrolyte in the device for storage of electrical energy. In addition, it is believed that among the ionic liquids with relatively low melting point of some ionic liquids lacks stability because they have low temperature thermal decomposition (see patent the th document 1 and non-patent documents 1 and 2).

Relative to the ionic liquid is stable in a wide temperature range, have been reported ionic liquid, which is formed using as a cation Navaho compounds containing a nitrogen atom represented by the ammonium cation. However, the ionic liquid containing the ammonium cation, has a relatively high melting point and viscosity, and only few of them have such a structure that provides a low viscosity fluid at approximately room temperature. (See patent document 2, patent document 3 and non-patent documents 3-6).

In other words, there are actually only a few ionic liquids that are stable in the liquid state in a wide temperature range, and the lack of excellent electrochemical stability is a big obstacle when the ionic liquid are trying to apply for lithium rechargeable batteries, capacitors, electric double layer (edlcs), fuel cells, solar cells based on sensitized inks or as the electrolyte, an electrolytic solution or an additive for devices, accumulating electrical energy.

Patent document 1: Publication of Japanese patent No. 2001-517205 intended for reference.

Patent document 2: publication of the international application is WO 02/076924.

Patent document 3: Japanese Publication patent No. 2003-331918 intended for reference.

Non-patent document 1: Rika Hagiwara, Electrochemistry, 70, № 2, 130 (2002).

Non-patent document 2: Y. Katayama, S. Dan, T. Miura and T. Kishi, Journal of The Electrochemical Society, 148(2), C102-C105 (2001).

Non-patent document 3: Hajime Matsumoto and Yoshinori Miyazaki, Yoyuen Oyobi Kouonkagaku, 44, 7(2001).

Non-patent document 4: H. Matsumoto, M. Yanagida, K. Tanimoto, M. Nomura, Y. Kitagawa and Y. Miyazaki, Chem. Lett, 8, 922(2000).

Non-patent document 5: D. R. MacFarlane, J. Sun, J. Golding, P. Meakin and M. Forsyth, Electrochimica Acta, 45,1271(2000), and

Non-patent document 6: Doulas R. MacFarlane, Jake Golding, Stewart Forsyth, Maria Forsyth and Glen B. Deacon, Chem. Commun., 1430(2001).

Description of the invention

Problem solved with the help of inventions

The purpose of the present invention is to obtain an ionic liquid, which is stable in the liquid state in a wide temperature range and has excellent electrochemical stability, and develop a method of producing an ionic liquid, and also in obtaining the ionic liquid, which is suitable for use as a material for the above-mentioned electrolytes, lithium rechargeable batteries, capacitors, electric double layer (edlcs), solar cells based on sensitized inks, fuel cells, solvents for the implementation of the reactions and the like, in particular in obtaining the ionic liquid, which is a hundred who think in a liquid state at approximately room temperature. More specifically, the purpose of the present invention is to obtain an ionic liquid, which contains a new cation of phosphonium.

A means for solving problems

The authors of the present invention have synthesized a number of salts consisting of a cationic component and an anionic component, and conducted intensive studies of ionic liquids in order to achieve the above mentioned goals. In the result it was found that the ionic liquid, which contains a phosphonium ion with one or more connections of the P-N as a cationic component, in particular, at least one kind selected from the group of organic cations represented by the following General formula (1), capable of forming ionic liquid, which is stable in a wide temperature range and has excellent electrochemical stability.

Chemical formula 1

In the above formula, the substituents R1-R11independent of each other and can be identical or different from each other. Each of the substituents R1-R11represents any one selected from a hydrogen atom, a C1-C30is an alkyl group with a linear or branched chain, C2-C30-alkenylphenol group with a linear or branched chain, containing one or more double bonds, C2-C3 -alkenylphenol group with a linear or branched chain, containing one or more triple relations, saturated or partially or fully unsaturated cycloalkyl group, aryl group and heterocyclic group. The hydrogen atoms contained in one or more of the substituents R1-R11may be partly or completely replaced by halogen atoms or partially replaced by a CN group or NO2-group. Any Deputy of the substituents R1-R11together with another Deputy may form a ring structure. The carbon atoms contained in the substituents R1-R11may be replaced by atoms and/or group of atoms selected from the group consisting of-O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O -, and-P(R')2=N-, in which R'represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group, or unsubstituted or substituted heterocycle. X1X2and X3independent from each other and represent a nitrogen atom, an oxygen atom, a sulfur atom or the volume of carbon. At the same time two of X1X2and X3can't imagine a nitrogen atom. R3, R8or R11is a Deputy, which is present in the formula, only when X1X2or X3represents a carbon atom. When X1represents a carbon atom, X1, R1, R2and R3together may form a saturated or partially or fully unsaturated ring structure; when X2represents a carbon atom, X2, R6, R7and R8together may form a saturated or partially or fully unsaturated ring structure; and when X3represents a carbon atom, X3, R9, R10and R11together may form a saturated or partially or fully unsaturated ring structure. In addition, R2, R7or R10is a Deputy, which is present in the formula, only when X1X2or X3represents a nitrogen atom or a carbon atom. When X1represents a nitrogen atom or a carbon atom, X1, R1and R2together may form a saturated or partially or fully unsaturated ring structure; when X2depict is to place a nitrogen atom or a carbon atom, X2, R6and R7together may form a saturated or partially or fully unsaturated ring structure; and when X3represents a nitrogen atom or a carbon atom, X3, R9and R10together may form a saturated or partially or fully unsaturated ring structure. In addition, the dotted lines show the coupled structure.

In other words, in the present invention receive the ionic liquid, which comprises a cationic component phosphonium ion with one, two or four-connected P-N; ionic liquid, which contains as the cationic component of the organic substance represented by the General formula (1); and ionic liquid, which comprises a cationic component and an anionic component, in which the cationic component is one or more kinds selected from the group of cationic components represented by the General formula (1), thereby achieving the above goal.

Brief description of drawings

The figure 1 shows a graph showing a CV curve for bistrifluormethylbenzene methylbutyl-bis(diethylamino)phosphonium according to example 2.

The figure 2 shows a graph showing a CV curve for bistrifluormethylbenzene dimethylbutyl(diethylamino)phosphonium on p is the emer 6.

The figure 3 shows a graph showing a CV curve for bistrifluormethylbenzene Tris(diethylamino)di-n-butylaminoethyl in example 13.

The best way of carrying out the invention

In the cation component represented by the General formula (1), the substituents R1-R11preferably should be any selected from a hydrogen atom, a C1-C30is an alkyl group with a linear or branched chain, saturated or partially or fully unsaturated cycloalkyl groups, aryl groups and heterocyclic groups, and hydrogen atoms contained in one or more of the substituents R1-R11must be partly or completely replaced by halogen atoms, or partially replaced by a CN group or NO2-group. Also preferably the carbon atoms contained in the substituents R1-R11should be replaced by atoms and/or group of atoms selected from the group consisting of

-O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O) -, and-NR'- (in which R'represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group or unsubstituted Il is substituted heterocycle). In yet another example, it is preferable that each of R1-R11in the General formula (1), which may be the same or different from each other, represents a C1-C20is an alkyl or alkoxy group with a linear or branched chain.

Examples of the anionic component used in the present invention include one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfS2)2N]-,[(RfSO2)3C]-, [(FS2)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(CF3)2]-, [N(CN)2]-, [AlCl4]-PF6-, [RfPF5]-, [Rf3PF3]-BF4-, [RfBF3]-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-in which the substituent R represents any one selected from a hydrogen atom, halogen atom, a C1-C10is an alkyl group with a linear or branched chain, C2-C10-alkenylphenol group linearly with the or branched chain, which contains one or more double bonds, C2-C10-alkenylphenol group with a linear or branched chain, containing one or more triple relations, and saturated or partially or fully unsaturated cycloalkyl group; hydrogen atoms contained in the substituent R may be partially or completely replaced by halogen atoms or partially replaced by a CN group or NO2group; the carbon atoms contained in the substituent R may be replaced by atoms and/or group of atoms selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NR'-, -N(R')2-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O -, and-P(R')2=N-, in which R'represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group or unsubstituted or substituted heterocycle; and Rf represents a fluorinated Deputy. These anionic components are combined with the above-mentioned cationic component and provide an ionic liquid, which is stable in the liquid state in a wide temperature range and has excellent the electrochemical stability. Used here, the term "ionic liquid is stable in the liquid state in a wide temperature range" means that the ionic liquid remains in a liquid state at approximately 100°C and has a temperature of thermal decomposition, which is higher than its melting point of approximately 200°C or more, which is now regarded as a common definition of ionic liquids. In other words, the ionic liquid is stable in the liquid state in this wide temperature range.

These anionic components as counterion, in combination with cationic component represented by the General formula (1)preferably represents one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfS2)2N]-, RfCOO-PF6-BF4-,[RfBF3]-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-and more preferably one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfS2)2N]-, RfCOO-PF6-BF4-, [RfBF3]-, [B(OR)4]-, [N(CN)2]-,

AlCl 4]-, SO42-, HSO4-and NO3-.

Combining the above-mentioned cationic component and the above-mentioned preferred anionic components provides even more in-demand properties, in other words, it provides the ionic liquid, which is stable in the liquid state in a wide temperature range from low temperatures, and has excellent electrochemical stability.

Particularly preferred ionic liquid is defined as follows: anionic component that is used as the counterion to the cationic component represented by the General formula (1)represents one or more kinds selected from the group consisting of [RSO3]-, [RfSO3]-, [(RfS2)2N]-, RfCOO-PF6-BF4-,[RfBF3]-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-, F-, Cl-, Br-and I-; and each of R1-R11in the General formula (1), which may be the same or different from each other and represents a hydrogen atom or a C1-C10is an alkyl or alkoxy group with a linear or branched chain.

In addition, by reducing the symmetry of CATIA is a, represented by the General formula, for example by carrying out selection so that among R1-R11at least one group different from others, you can get an ionic liquid with a low melting point.

In the case when you want the ionic liquid with a low melting point, may be mentioned ionic liquid, which contains cationic component is defined as follows: at least one of R1-R11in the General formula (1) represents a C4-C20is an alkyl or alkoxy group with a linear or branched chain, and the remaining Rnrepresent a hydrogen atom or a C1-C4is an alkyl group with a linear chain, or another ionic liquid, which contains cationic component is defined as follows: at least one of R1-R11represents a silyl group, or has a ring structure, and the remaining Rnrepresent a hydrogen atom or a C1-C4is an alkyl group with a linear chain. Particularly preferred example of Association includes the cation of phosphonium, which is defined as follows: X1X2and X3represent a carbon atom; R1represents various group; R2and R3represent a carbon atom; R4and R5pre whom represent ethyl group; and R6-R11represent a hydrogen atom; one cation of phosphonium, which is defined as follows: X1X2and X3represent a nitrogen atom; R1and R2are boutelou group; and R4, R5, R6, R7, R9and R10represent an ethyl group; another cation of phosphonium, which is defined as follows: X1X2and X3represent a nitrogen atom; R1, R2, R4, R6and R9represent a methyl group; and R5, R7and R10are boutelou group; another cation of phosphonium, which is defined as follows: X1X2and X3represent a nitrogen atom; R1and R2represent an ethyl group; R4, R6and R9represent a methyl group; and R5, R7and R10are boutelou group, etc.

In addition, supporting examples the effect of reducing the symmetry of the cation at the melting point are the following facts. The melting point of the ionic liquid consisting of a cation, where X1X2and X3represent a nitrogen atom, and all R1, R2, R4, R5, R6, R7, R9and R10represent an ethyl group; and anion (C 3SO2)2N-of approximately 90°C. on the other hand, the melting point of the ionic liquid consisting of a cation, where X1X2and X3represent a nitrogen atom, R1and R2are boutelou group; and R4, R5, R6, R7, R9and R10represent an ethyl group; and anion (CF3SO2)2N-approximately 25°C. Therefore, when reducing the symmetry of the melting point lowered by about 65°C.

As the anionic component that is combined with these cations, mention can be made of any of (CF3SO2)2N-PF6-and BF4-and particularly preferred is (CF3SO2)2N-or BF4-. As mentioned above, the ionic liquid with a low melting point can be used in pure form in the electrolyte or as a solvent for performing reactions at low temperature, increasing the scope of applications of ionic liquids.

The above-mentioned ionic liquid of the present invention is stable in a wide temperature range and has excellent electrochemical stability. Therefore, the ionic liquid according to the present invention has been successfully used as the electrolyte, power is imicheskogo solution, the additive or the like devices, accumulating electrical energy, as a material for rechargeable lithium batteries, capacitors, electric double layer (edlcs), fuel cells or solar cells based on sensitized inks, drivers or lubricating oil, or as a solvent for various reactions. In addition, the ionic liquid of the present invention is also stable with respect to strong alkali, so that it can be used as a solvent for performing reactions under alkaline conditions. It is known that in the case of the use of ionic liquids instead of traditional plasticizers thermal stability is significantly increased.

Reported electrolytic deposition of aluminum or aluminum alloys such as Al-Mn, Al-Ti, Al-Mg and Al-Cr, of the ionic liquid.

By polymerization of ionic liquid can be developed polymeric material, which has unique properties of ionic liquids with high density of ions, such as slowing down the spread of flames and electrochemical stability.

Note that the cation of the General formula (1) are presented in the form of a cation of phosphonium, with the positive charge localized on the phosphorus atom, but it is thought that the molecule charge is delocalized.

p> A typical method for the synthesis of ionic liquid, which contains a cation component represented by the General formula (1)described below.

Chemical formula 2

The organic substance used as starting material represented by the General formula (2) or (3), added dropwise alkylating agent (R7W) and the resulting mixture is subjected to interaction at a given temperature for a specified time. The obtained reaction product was washed with ultrapure water or simple diethyl ether, etc. and then dried in vacuum. As the alkylating agent (R7W) mentions alkylated, allylbromide, alkylchloride, sulfate complex dialkylamide ether, sulfonate complex dialkylamide ether, carbonate complex dialkylamide ether phosphate complex trialkylated ether, alkylanthraquinones, alkylpolyglycoside, alkylarylsulfonate, alkylaminocarbonyl, alkylpolyglucosides, alkylphenolethoxylate, sulfuric acid, nitric acid, hydrochloric acid, etc.

The ionic liquid containing a cationic component, which contains four links P-N and represented by the General formula (1)receive, for example, as follows.

Chemical formula 3

In the above formula, R1 may be the same as R2.

The organic substance used as starting material represented by the General formula (4), added dropwise alkylating agents (R1W and R2W) and the resulting mixture is subjected to interaction at a given temperature for a specified time. The obtained reaction product was washed with ultrapure water or simple diethyl ether, etc. and then dried in vacuum. In kazacestva alkylating agents (R1W and R2W) mentions alkylated, allylbromide, alkylchloride, sulfate complex dialkylamide ether, sulfonate complex dialkylamide ether, carbonate complex dialkylamide ether phosphate complex trialkylated ether, alkylanthraquinones, alkylpolyglycoside, alkylarylsulfonate, alkylphenolethoxylate, alkylpolyglucosides, alkylphenolethoxylate, sulfuric acid, nitric acid, hydrochloric acid, etc.

In addition, you can also get ionic liquids with different anions, for example, by anion exchange as described below.

Chemical formula 4

Here as ionic compounds A+Q are mentioned, for example, LiN(CF3SO2)2, NaN(CF3SO2)2, KN(CF3SO2)2, CF3SO3Li, CF3SO3 Na, CF3CF2CF2CF2SO3Li, CF3SO3K, CF3CH2SO3Li, CF3CH2SO3Na, CF3CH2SO3K, CF3COOLi, CF3COONa, CF3COOK, CF3COOAg, CF3CF2CF2COOAg, LiPF6, NaPF6, KPF6, LiBF4, NaBF4, KBF4, NH4BF4, KC2F5BF3, LiB(C2About4)2, LiSbF6, NaSbF6, KSbF6, NaN(CN)2, AgN(CN)2, Na2SO4, K2SO4, NaNO3, KNO3and so on, however, the ionic compound is not limited to the above compounds.

The substituents R1-R7in the General formula (5) and the substituents R1, R2, R4-R7, R9and R10in the General formula (6) independently can be the same or different from each other. Each of these substituents represents any one selected from a hydrogen atom, halogen atom, a C1-C30is an alkyl group with a linear or branched chain, C2-C30-alkenylphenol group with a linear or branched chain, containing one or more double bonds, C2-C30-alkenylphenol group with a linear or branched chain, containing one or more triple relations, saturated or partially or fully unsaturated cycloalkyl group, aryl group and a heterocycle which political group. The hydrogen atoms contained in one or more of the substituents may be partially or completely replaced by halogen atoms or partially replaced by a CN group or NO2-group. Any Deputy of the substituents R1-R7or any Deputy of the substituents R1, R2, R4-R7, R9and R10may form a ring structure together with another Deputy. The carbon atom contained in these substituents may be replaced by atoms and/or group of atoms selected from the group consisting of-O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=,

-N=N-, -NH-, -NR'-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O -, and-P(R')2=N-, in which R'represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted phenyl group or unsubstituted or substituted heterocycle.

As described above, the halogen atom mentioned fluorine, chlorine, bromine and iodine.

As described above cycloalkyl groups mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cycloneii, cyclodecyl etc. Cycloalkyl groups which includes a group, containing unsaturated bond, such as cycloalkenyl group and cycloalkenyl group. Cycloalkyl group may be partially or completely replaced by halogen atom, or may be partially replaced by a CN group or NO2group.

As described above heterocyclic groups mentioned pyridinyl, Pasolini, imidazolidinyl, imidazolyl, pyrazolidine, personal, piperidyl, piperazinyl, morpholinyl, thienyl etc. These heterocyclic groups can contain one or more groups selected from alkyl, alkoxy, hydroxyl, carboxyl, amino, alkylamino, dialkylamino, tylnej and alkylthio and halogen atom.

As described above aryl groups mentioned phenyl, cominella, mesitylene, Tomilina, xylella, etc. groups. These aryl groups may contain one or more groups selected from alkyl, alkoxy, hydroxyl, carboxyl, acyl, formyl, amino, alkylamino, dialkylamino, tylnej, alkylthio groups, and halogen atoms.

There is also mention of alkoxyalkyl group, such as methoxymethyl, methoxyaniline, ethoxymethylene and amoxicilina, trialkylsilyl group, such as trimethylsilyl group, etc.

As the anionic component Q, which are allowed to interact and joint shall apply with the connection, represented by the General formula (4) or (5), mentioned anionic described above components.

Examples

The present invention will be described in detail with reference to the following examples, but the examples in any case should not be interpreted as limiting the present invention.

Example 1

(a) Obtaining chlorobis(diethylamino)phosphine

In a 300 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 10.0 g (0,0728 mol) of trichloride phosphorus and 100 ml of anhydrous simple diethyl ether and cooled the mixture to 5°C or below in a bath with ice. As stirring the obtained reaction mixture to the reaction mixture for 3 hours slowly was added dropwise 30,0 ml (0,291 mol) of diethylamine. The obtained crystals were filtered under pressure in the atmosphere of nitrogen gas. After the crystals are washed three times simple anhydrous diethyl ether, was purified by vacuum distillation (0,4 kPa, 77,8-78,2°C), while receiving 8,07 g chlorobis(diethylamino)phosphine in the form of a transparent liquid; the yield was 53%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The spectral d is installed below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,20-3,24 (m, 8H), 1.14 in (t, 12H)

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 160,56 (s, 1P)

The structural formula is shown below.

Chemical formula 5

(b) Obtaining methylbis(diethylamino)phosphine

200 ml chetyrehosnuju flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 8,07 g (of 0.038 mol) chlorobis(diethylamino)phosphine obtained in (a), and 100 ml of anhydrous simple diethyl ether and cooled the mixture to -78°C. as stirring the obtained reaction mixture to the reaction mixture was added dropwise 38 ml of a 1 mol/l CH3Li in simple diethyl ether. After further stirring the reaction mixture for 15 minutes, the temperature was slowly increased and then boiling the reaction mixture under reflux for 45 minutes. After the temperature was returned to room temperature, the resulting crystals were filtered under pressure in an atmosphere of gaseous nitrogen and then washed three times simple anhydrous diethyl ether. The crystals were additionally purified by vacuum distillation (0,4 kPa, and 63.9-65,7°C), while receiving 5.10 g m is tivis(diethylamino)phosphine in the form of a transparent liquid; the yield was 71%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,05 of 2.92 (m, 8H), 1.26 in (d, 3H), 1.00 m (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 79,19 (m, 1P).

The structural formula is shown below.

Chemical formula 6

(C) Obtaining the methyl sulfate dimetilan(diethylamino)phosphonium

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 2,82 g (0,0148 mol) methylbis(diethylamino)phosphine obtained in (b), the mixture was cooled with ice and then added dropwise 1.7 ml (0.018 mol) of dimethylsulfate. After stirring the reaction mixture at room temperature for 4 hours, it was thrice washed simple diethyl ether. By vacuum drying at room temperature was received of 4.25 g of the methyl sulfate dimetilan(diethylamino)phosphonium in the form of a white solid; yield was 91%.

The compound obtained was identified using the analyzer on the basis of nuclear magnitno the resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,98 (s, 3H), 3,20-is 3.08 (m, 8H), and 2.14 (d, 6N), 1,19 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 62,19 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 7

(d) Obtaining bistrifluormethylbenzene dimetilan(diethylamino)phosphonium

In a 100 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 4,25 g (0,0134 mol) of methyl sulfate dimetilan(diethylamino)phosphonium obtained in (c), and 25 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution, which is 4.2 g (0.015 mol) of LiTFSI dissolved in 25 ml of ultrapure water, and the resulting mixture was further stirred at room temperature for 15 hours. The obtained salt was extracted with 50 ml of CH2Cl2. The aqueous layer was additionally extracted with 50 ml of CH2Cl2. The organic layer is washed three times with 100 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. this produces what and 4.77 g of bistrifluormethylbenzene dimetilan(diethylamino)phosphonium in the form of white solids; the yield was 73%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,15 totaling 3.04 (m, 8H), 1,95 (d, 6N), 1,17 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,93(s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 59,70 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 8

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal 38,7°C, and the crystallization temperature was equal to 29.4°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 398,6°C.

Example 2

(e) Receivingn-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium

In 50 ml of dvuhgolosy flask, equipped with magnetic m is szalkai, at room temperature in an atmosphere of gaseous nitrogen was loaded 2.28 g (0.012 mol) methylbis(diethylamino)phosphine obtained in (b), the mixture was cooled with ice and then was added dropwise to 2.85 ml (0,0144 mol) di-n-butylsulfide. After stirring the reaction mixture at room temperature for 21 hours it washed three times simple diethyl ether and dried in vacuum at room temperature, while receiving 3.13 gn-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium in the form of a yellow liquid: yield was 65%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ is 4.03 (t, 2H), 3,20-is 3.08 (m, 8H), 2,47-is 2.37 (m, 2H), 2,12 (d, 3H), 1,67 to 1.37 (m, 8H), 1,19 (t, N), of 0.97 (t, 3H), of 0.91 (t, 3H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 65,23 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 9

(f) Obtaining bistrifluormethylbenzene methyl-nRutilus(diethylamino)phosphonium

100 m the flask from trap to trap, equipped with a magnetic stirrer, was loaded 3.13 g (0,0078 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium obtained in paragraph(e), and 25 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution in which 25 ml of ultrapure water was dissolved 2.5 g (0,0086 mol) LiTFSI, and the resulting mixture was further stirred at room temperature for 15 hours. The obtained salt was extracted with 50 ml of CH2Cl2. The aqueous layer was additionally extracted with 50 ml of CH2Cl2. The organic layer is washed three times with 100 ml of ultrapure water, and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. When this got to 3.02 g of bistrifluormethylbenzene methyl-n-Rutilus(diethylamino)phosphonium in the form of a transparent liquid; the yield was 73%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,15 totaling 3.04 (m, 8H), 2,27-to 2.18 (m, 2H), 1.91 a (d, 3H), 1,55-of 1.42 (m, 4H), of 1.18 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard is emesto: CF 3Cl) δ -78,86 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 62,86 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 10

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 15.9°C, and the crystallization temperature was equal situated 10.5°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 394,3°C.

Electric conductivity was measured by AC impedance method (system for electrochemical measurements HZ-3000, made by Hokuto Denko Corp.), equal 0,088 Cm-1at 25°C.

Electrochemical window was in the range from minus 0.1 V to 4.7 In relative to Li/Li+, which was obtained from cyclic voltammogram measured using the system for electrochemical measurements HZ-3000 production company Hokuto Denko Corp., using Pt as the working electrode and counter-electrode and Li as a reference electrode. The CV curve of bistrifluormethylbenzene methyl-n-Buti is bis(diethylamino)phosphonium shown in figure 1.

(g) Receiving tetrafluoroborate methyl-n-Rutilus(diethylamino)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 2,00 g (0,0050 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e), and 10 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 0.6 g (0,0055 mol) NH4BF4and the resulting mixture was additionally stirred at room temperature for 15 hours. The obtained salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 50 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 0,93 g tetrafluoroborate methyl-n-Rutilus(diethylamino)phosphonium in the form of a white solid; yield was 53%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) is of 3.12 (m, 8H), 2,28 (m, 2H), 1,97 (d, 3H), 1,57 of 1.46 (m, 4H), of 1.18 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -152,51 (d, 4F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 63,80 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 11

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 16.9°C, and the crystallization temperature was equal to -19,9°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 363,0°C.

(h) Receiving hexaphosphate methyl-n-Rutilus(diethylamino)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 2,00 g (0,0050 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e), and 10 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 0.84 g (0,0055 mol) LiPF6 and the resulting mixture was additionally stirred at room temperature for 15 hours. The obtained salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 50 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 1.78 g of hexaflurophosphate methyl-n-Rutilus(diethylamino)phosphonium in the form of a white solid; yield 83%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,11 (m, 8H), of 2.23 (m, 2H), 1,92 (d, 3H), 1,58 was 1.43 (m, 4H), of 1.18 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -72,75 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 63,80 (m, 1P),-144,29 (cept, 1P).

The structural formula shown below (in the formula, the dotted line shows the coupled structure).

Chemical formula 12

The melting point was measured using the differential scanning calorimeter (DSC8230, production company Shimadzu Corp.). The melting point was $ 140,0°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 373,0°C.

Example 3

(i) Obtaining bis(diethylamino)(trimethylsilylmethyl)phosphine

In a 50 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 0.36 g (of 14.8 mmol) of magnesium and 10 ml of anhydrous simple diethyl ether. After adding a few drops of 1,2-dibromoethane to activate magnesium caution was added dropwise 2.0 ml (of 14.2 mmol) of chlorotetracycline to avoid heating. When the reaction solution was stirred for 1 hour as it is slightly heated with a drier, the solution was made dark. Then, after cooling the solution to -78°C the solution was added dropwise 3.0 g (of 14.2 mmol) chlorobis(diethylamino)phosphine, synthesized under item(a), and then the resulting mixture was heated to room temperature and boiled under reflux for 1 hour. The obtained crystals were filtered off, washed simple anhydrous diethyl ether and was purified by vacuum distillation (0.2 kPa, 74,3-of 79.5°C), while this is to 2.29 g of bis(diethylamino)(trimethylsilylmethyl)phosphine in the form of a colorless transparent liquid; the yield was 62%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,98 (m, 8H), of 0.95 (m, 14N), 0,00 (s, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 84,01 (s, 1P)

The structural formula is shown below.

Chemical formula 13

(j) Obtaining methyl sulfate bis(diethylamino)(methyl)(trimethylsilylmethyl)phosphonium

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen loaded to 1.15 g (0,0044 mol) of bis(diethylamino)(trimethylsilylmethyl) phosphine obtained under item(i), cooled with ice and then was added dropwise to 0.50 ml (0,0053 mol) dimethylsulfate. After stirring the reaction mixture at room temperature for 18 hours, washed it three times simple diethyl ether. The reaction mixture was dried in vacuum at room temperature, while receiving of 1.34 g of methyl sulfate bis(diethylamino)(methyl)(trimethylsilylmethyl)phosphonium in the form of a white solid; yield was 79%.

Received connection ID which was tificially analyzer based on nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,49 (s, 3H), 3.33 and-3,20 (m, 8H), 2,27-of 2.16 (m, 5H), to 1.21(t, N), 0,30 (s, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 62,07 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 14

(K) Obtaining bistrifluormethylbenzene bis(diethylamino)(methyl)(trimethylsilylmethyl)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded to 1.34 g (0,0035 mol) of methyl sulfate bis(diethylamino)(methyl)(trimethylsilylmethyl)phosphonium received under item(j), and 10 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 1.1 g (0,0038 mol) LiTFSI, and the resulting mixture was further stirred at room temperature for 15 hours. The obtained salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 20 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a Roto the aqueous evaporator and dried in vacuum at 80°C. It was obtained 1.13 g of bistrifluormethylbenzene bis(diethylamino)(methyl)(trimethylsilylmethyl)phosphonium in the form of a transparent liquid; the yield was 58%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ to 3.09 (m, 8H), was 1.94 (d, 3H), 1.70 to (d, 2H), 1,17 (t, N), and 0.25 (s, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,78 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 60,62 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 15

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal 32,1°C. the crystallization Temperature was equal to 12.2°C. the transition Temperature in the glassy state was equal to -65,8°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, change the military at a rate of temperature increase of 10°C/min, equal 229,8°C.

Example 4

(1) Obtaining bistrifluormethylbenzene 1,1-bis(diethylamino)-3-methyl-3-vospolenie

In a 200 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 1,90 g (0,0142 mol) of aluminium chloride and 30 ml of anhydrous dichloromethane. When cooled with ice was added dropwise a solution, in which 25 ml of anhydrous dichloromethane is dissolved 3.0 g (0,0142 mol) chlorobis(diethylamino)phosphine, synthesized under item(a). After stirring the reaction mixture for 1 hour and cooling it to 0°C was added dropwise to 1.42 ml (0,0142 mol) of isoprene. The reaction mixture was stirred at room temperature for 1 hour. Then to the reaction mixture was added 4.5 g (0,016 mol) LiTFSI and the resulting mixture was stirred at room temperature overnight. Then the reaction mixture was washed with ultrapure water until such time as will not be detected turbidity. The obtained organic layer was concentrated using a rotary evaporator, washed three times simple diethyl ether, dried in vacuum at 80°C, while receiving 0,94 g bistrifluormethylbenzene 1,1-bis(diethylamino)-3-methyl-3-vospolenie in the form of white crystals; yield was 13%.

The compound obtained was identified using analisado is based on the nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 5,69 (d, 1H), 3.15 in (m, 8H), 3.00, it is only 2.91 (m, 4H), of 1.92 (s, 3H), 1,19 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,87 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 81,46 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 16

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was 33.3°C. the crystallization Temperature was equal to 22.1°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 346,1°C.

Example 5

(m) Receiving chloro(N,N'-dimethylethylenediamine)phosphine

In a 1000 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen loaded to 31.9 g (0,233 mol) of trichloride phosphorus and 500 ml of anhydrous simple dietro the CSOs ether and cooled the mixture to 5°C or below in a bath with ice. As stirring the obtained reaction mixture to the reaction mixture slowly dropwise added to 25.0 ml (0,233 mol) N,N'-dimethylethylenediamine. In addition, slowly dropwise added 65,0 ml (0,465 mol) of triethylamine. After further stirring the reaction mixture for 1.5 hours, it was filtered in an atmosphere of nitrogen gas. After the obtained crystals are washed three times simple anhydrous diethyl ether, was purified by vacuum distillation (0,4 kPa, 44-52°C), while receiving 16.28 per g of chloro(N,N'-dimethylethylenediamine)phosphine in the form of a transparent liquid; the yield was 46%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.32 (d, 4H), 2,78 (d, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 171,30 (s, 1P).

The structural formula is shown below.

Chemical formula 17

(n) to Obtain methyl(N,N'-dimethylethylenediamine)phosphine

200 ml chetyrehosnuju flask, equipped with reflux condenser, addition funnel and magnetic michalko is, at room temperature in an atmosphere of gaseous nitrogen was loaded 8.00 g (0,0524 mol) chloro(N,N'-dimethylethylenediamine)phosphine obtained under item(m), and 100 ml of anhydrous simple diethyl ether and cooled the mixture to -78°C. as stirring the obtained reaction mixture to the reaction mixture was added dropwise 53 ml of 1 mol/l solution of CH3Li in simple diethyl ether. As additional stirring the reaction mixture temperature was slowly increased, and then the reaction mixture is boiled under reflux for 1 hour. After the temperature was returned to room temperature, the resulting crystals were filtered under pressure in the atmosphere of nitrogen gas, and then washed three times simple anhydrous diethyl ether. The crystals were purified by vacuum distillation (4.6 kPa, 62,3°C), while receiving 3,76 g of methyl(N,N'-dimethylethylenediamine)phosphine in the form of a transparent liquid; the yield was 54%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,21-and 3.16 (m, 2H), 3,01-2,96 (m, 2H), 2,64 (d, 6N), to 0.89 (d, 3H).

31P-NMR (121 MHz, RA is the solvent: CDCl 3standard substance: triphenylphosphine) δ 118,38 (s, 1P).

The structural formula is shown below.

Chemical formula 18

(a) Obtaining iodide

methyl-n-butyl-(N,N'-dimethylethylenediamine)phosphonium

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 0,80 g (0,0061 mol) of methyl-(N,N'-dimethylethylenediamine)phosphine obtained under item(n), cooled with ice and then added dropwise to 1.15 g (0,0062 mol)n-butylidene. After stirring the reaction mixture at room temperature for 16 hours and washed it three times simple diethyl ether. By vacuum drying at room temperature was received of 1.65 g of methyl iodide-n-butyl-(N,N'-dimethylethylenediamine)phosphonium in the form of a white solid; yield was 86%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: D2O, standard substance:

2,2-dimethyl-2-silapentane-5-sulfonate) δ 3,28 (d-d, 4H), 2,68 (d, 6N), 2,24 (m, 2H), of 1.75 (d, 3H), 1,39-of 1.30 (m, 4H), 0,81 (t, 3H).

31P-NMR (121 MHz, solvent: D2O standard in the society: triphenylphosphine) δ 80,69 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 19

(p) Obtaining bistrifluormethylbenzene methyl-n-butyl-(N,N'-dimethylethylenediamine)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 1,65 g (0,0052 mol) of methyl iodide-n-butyl-(N,N'-dimethylethylenediamine)phosphonium received under item (o), and 10 ml of ultrapure water. As stirring the obtained reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 1.7 g (0,0057 mol) LiTFSI, and the resulting mixture was further stirred at room temperature for 15 hours. The obtained salt was extracted with 20 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 20 ml of ultrapure water, and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 0.31 g of bistrifluormethylbenzene methyl-n-butyl-(N,N'-dimethylethylenediamine)phosphonium in the form of a transparent liquid; the yield was 13%.

The compound obtained was identified using the analyzer on the basis of nuclear magnetic resonance (JV shall chromer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,38 (d-d, 4H), 2,80 (d, 6N), and 2.27 (m, 2H), of 1.84 (d, 3H), 1,47-of 1.36 (m, 4H), of 0.93 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,95 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 80,66 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 20

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 30.7°C. the crystallization Temperature was equal to 5.9°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 337,2°C.

Example 6

(q) Receiving dichloro(diethylamino)phosphine

In a 300 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded with 6.0 ml (0,069 mol) of trichloride phosphorus and 100 ml of anhydrous diethyl simple e the Ira and cooled the mixture to 5°C or less in a bath with ice. As stirring the obtained reaction mixture was slowly dropwise added to 7.1 ml (0,069 mol) of diethylamine for 3 hours. The reaction mixture was filtered under pressure in the atmosphere of nitrogen gas. The resulting crystals are washed three times simple anhydrous diethyl ether and was purified by vacuum distillation (0,4 kPa and 27.3-28.2°C), while receiving at 6.84 g of dichloro(diethylamino)phosphine in the form of a transparent liquid; the yield was 57%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,40 be 3.29 (m, 4H), 1,19 (t, 8H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 162,67 (s, 1P).

The structural formula is shown below.

Chemical formula 21

(r) to Obtain dimethyl(diethylamino)phosphine

200 ml chetyrehosnuju flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 5,23 g (0,0312 mol) of dichloro(diethylamino)phosphine obtained in p.(q), and 60 ml of anhydrous simple diethyl ether and cooled with the offer to -78°C. As stirring the reaction mixture to the reaction mixture was added dropwise 60 ml of 1 mol/l solution of CH3Li in simple diethyl ether. Then the reaction mixture was additionally stirred for 15 minutes, slowly raise the temperature and then the reaction mixture is boiled under reflux for 45 minutes. After the temperature was returned to room temperature, the resulting crystals were filtered under pressure in the atmosphere of nitrogen gas, and then washed three times simple anhydrous diethyl ether. The crystals were purified by vacuum distillation (10,8 kPa, 69,5-70,0°C), while receiving of 1.87 g of dimethyl(diethylamino)phosphine in the form of a transparent liquid; the yield was 45%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,97-of 2.86 (m, 4H), of 1.09 (d, 6N), 1,01 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 35,04 (m, 1P).

The structural formula is shown below.

Chemical formula 22

(s) Receivingnbutylsulfide dimethyl-n-butyl(diethylamino is)phosphonium

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen download of 0.62 g (0,0046 mol) dimethyl(diethylamino)phosphine obtained under item(r), cooled with ice and then was added dropwise 1.1 ml (0,0056 mol) di-n-butylsulfide. After stirring the reaction mixture at room temperature for 42 hours it washed three times simple diethyl ether. By vacuum drying at room temperature was obtained 1.18 gn-butylsulfide dimethyl-n-butyl(diethylamino)phosphonium in the form of a white solid; yield 75%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: acetone-d6standard substance: tetramethylsilane was) δ of 3.85 (t, 2H), 3.27 to (m, 4H), of 2.53 (m, 2H), 2,16 (d, 6N), 1,62-of 1.39 (m, 8H), 1,19 (t, 6N), 0,98-0,88 (m, 6N).

31P-NMR (121 MHz, solvent: acetone-d6standard substance: triphenylphosphine) δ 61,67 (m, 1P).

The structural formula is shown below.

Chemical formula 23

(t) the Receipt of bistrifluormethylbenzene dimethyl-n-butyl(diethylamino)phosphonium

In a 100 ml flask with a trap for trapping, borudovany magnetic stirrer, download 1,15 g (0,0034 mol)n-butylsulfide dimethyl-n-butyl(diethylamino)phosphonium received under item(s), and 25 ml of ultrapure water. As stirring the reaction mixture to the reaction mixture were added an aqueous solution in which 25 ml of ultrapure water was dissolved 1.2 g (0,0042 mol) LiTFSI, and the resulting mixture was further stirred at room temperature for 14 hours. The obtained salt was extracted with 50 ml of CH2Cl2and the aqueous layer was additionally extracted with 50 ml of CH2Cl2. After the obtained organic layer is washed three times with 100 ml of ultrapure water, extracted solution was concentrated with a rotary evaporator and dried in vacuum at 80°C. thus was obtained 1.39 g of bistrifluormethylbenzene dimethyl-nbutyl(diethylamino)phosphonium in the form of a transparent liquid; the yield was 87%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10 (m, 4H), 2,19 (m, 2H), 1.91 a (d, 6N), to 1.48 (m, 4H), 1,17 (t, 6N), of 0.95 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,93 (s, 6F).

31P-I Is R (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 59,45 (m, 1P).

The structural formula is shown below.

Chemical formula 24

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal -1,1°C. the crystallization Temperature was equal to -19,1°C. the transition Temperature in the glassy state was equal to -77,3°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 284,0°C.

Electric conductivity was measured by AC impedance method (system for electrochemical measurements HZ-3000, made by Hokuto Denko Corp.), equal 0,123 Cm-1at 25°C.

Electrochemical window ranged from 0 to 4.7 In respect to Li/Li, which was obtained from cyclic voltammogram measured using the system for electrochemical measurements HZ-3000 production company Hokuto Denko Corp., using a Pt working electrode and counter-electrode and Li reference electrode. The CV curve of bistrifluormethylbenzene dimethyl-n-butyl(diethylamino)phosphonium shown in figure 2.

(u) Receiving GE is superphosphate dimethyl- n-butyl(diethylamino)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 1,00 g (0,0029 mol)n-butylsulfide dimethyl-n-butyl(diethylamino)phosphonium received under item(s), and 10 ml of ultrapure water. As stirring the reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 0,49 g (0,0032 mol) LiPF6and the resulting mixture was additionally stirred at room temperature for 14 hours. The obtained salt was extracted with 20 ml of CH2Cl2. The aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 50 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 0,62 g hexaphosphate dimethyl-n-butyl(diethylamino)phosphonium in the form of a transparent liquid; the yield was 46%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10 (m, 4H), 2,19 (m, 2H), 1.91 a (d, 6N), to 1.48 (m, 4H), 1,17 (t, 6N), of 0.95 (t, 3H).

19F-I Is R (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -71,70 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 59,94 (m, 1P), -144,24 (cept, 1P).

The structural formula is shown below.

Chemical formula 25

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 138,1°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, equal is 317.1°C.

(v) Obtaining bis(oxalato)of methyl borate-n-Rutilus(diethylamino)phosphonium

In a 100 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 1,33 g (0,0033 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e), and 10 ml of acetonitrile. As stirring the reaction mixture to the reaction mixture was added a solution in which 30 ml of acetonitrile was dissolved 0.64 g (0,0033 mol) of bis(oxalate)lithium borate, and the resulting mixture was further stirred at room temperature for 2 days. Precipitated precipitated salt was filtered and the solution was concentrated in vacuum using Tarnovo evaporator. The obtained concentrate was dissolved in dichloromethane. After the resulting solution was washed three times with 100 ml of ultrapure water, extracted solution was concentrated in vacuo using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 1.25 g of bis(oxalato)of methyl borate-n-Rutilus(diethylamino)phosphonium in the form of a transparent liquid; the yield was 87%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ is 3.08 (m, 8H), 2,22 (m, 2H), 1.91 a (d, 3H), of 1.46 (m, 4H), of 1.16 (t, N), were 0.94 (t, 3H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 62,40 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 26

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -52,9°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, the production company Rigak Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was at 284.3°C.

(w) Receiving trevorcurrent methyl-n-Rutilus(diethylamino)phosphonium

In a 30 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 0.50 g (0,0013 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e). When the stirring was further added to the solution, in which 10 ml of ultrapure water was dissolved 0.20 g (0,0014 mol) trevorcurrent lithium. The resulting reaction mixture was additionally stirred at room temperature for 20 hours. After removal of the aqueous layer of the reaction mixture three times washed with ultrapure water and then dried in vacuum at 80°C. thus was obtained 0,23 g trevorcurrent methyl-n-Rutilus(diethylamino)phosphonium in the form of a white solid; yield was 46%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.12 (m, 8H), 2,33 (m, 2H), 2,02 (d, 3H), 1,50 (m, 4H), 1,19 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3that standard is e substance: CF 3Cl) δ -78,28 (s, 3F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 62,21 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 27

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 74,8°C. the transition Temperature in the glassy state was equal of 56.4°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 311,8°C.

(x) Receiving PERFLUORO-n-butylsulfonyl methyl-n-Rutilus(diethylamino)phosphonium

In a 30 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 0.50 g (0,0013 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e). When the stirring was further added to the solution, in which 5 ml of ultrapure water was dissolved 0,42 g (0,0014 mol) of PERFLUORO-n-butylsulfonyl lithium. The resulting reaction mixture was additionally stirred at room temperature for 16 hours. After removal of the aqueous layer of the reaction is th mixture thrice washed with ultrapure water and then dried in vacuum at 80°C. When this was received of 0.54 g of PERFLUORO-n-butylsulfonyl methyl-n-Rutilus(diethylamino)phosphonium in the form of a transparent liquid; the yield was 79%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.12 (m, 8H), 2,32 (m, 2H), 2,02 (d, 3H), 1,49 (m, 4H), of 1.18 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -80,91 (t-t, 3F), -114,71 (m, 2F), -121,63 (m, 2F), -125,99 (m, 2F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 64,09 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 28

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was $ 6.1°C. the crystallization Temperature was equal to -19,2°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a speed of raising the temperature is s 10°C/min, equal 328,8°C.

(y) the Receipt of pentafluoropropionate methyl-n-Rutilus(diethylamino)phosphonium

In a 30 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded 0,50 (0,0013 mol)n-butylsulfide methyl-n-Rutilus(diethylamino)phosphonium received under item(e). When the stirring was further added to the solution, in which 5 ml of ultrapure water was dissolved 0.31 g (0,0014 mol) of pentafluoropropionate potassium. The resulting reaction mixture was additionally stirred at room temperature for 20 hours. After removal of the aqueous layer of the reaction mixture is washed three times with 100 ml of ultrapure water and then dried in vacuum at 80°C. thus was obtained 0,48 g pentafluoropropionate methyl-n-Rutilus(diethylamino)phosphonium in the form of a white solid; yield was 88%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10 (m, 8H), 2,22 (m, 2H), 1.91 a (d, 3H), of 1.48 (m, 4H), 1,17 (t, N), of 0.97 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -83,80 (q, 3F), -136,81 (q, 2F), -154,33 (q, 2F).

31P-YAM who (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 63,38 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 29

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to a 126.7°C. the crystallization Temperature was equal to 120,6°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 289,6°C.

Example 8

(z) Obtaining chloro-(N,N'-dimethyl-1,3-Propylenediamine)phosphine

In a 1000 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen download of 4.2 ml (0,049 mol) of trichloride phosphorus and 300 ml of anhydrous simple diethyl ether and cooled the mixture to 5°C or below in a bath with ice. As stirring the reaction mixture to the reaction mixture slowly dropwise added 5 g (0,049 mol) N,N'-dimethyl-1,3-Propylenediamine. In addition, slowly was added dropwise 14 ml (0,098 mol) of triethylamine. After stirring the reaction mixture at room temperature is PE within 2 hours the reaction mixture was filtered under pressure in the atmosphere of nitrogen gas. The resulting crystals are washed three times simple anhydrous diethyl ether and then purified them by vacuum distillation (0.7 kPa, 90°C), while receiving 2,30 g of chloro-(N,N'-dimethyl-1,3-Propylenediamine)phosphine in the form of a transparent liquid; the yield was 29%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,00 (m, 4H), 2,68 (d, 6N), 1,90 (m, 2H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 161,10 (s, 1P).

The structural formula is shown below.

Chemical formula 30

(aa) the Receipt of methyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphine

200 ml chetyrehosnuju flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 2.30 g (0.014 mol) of chloro-(N,N'-dimethyl-1,3-Propylenediamine)phosphine obtained in p.(z), and 120 ml of anhydrous simple diethyl ether and cooled the mixture to -78°C. as stirring the reaction mixture to the reaction mixture was added dropwise 14 ml of 1 mol/l solution of CH3Li in simple the m diethyl ether. As stirring the reaction mixture was slowly raised the temperature and then the reaction mixture is boiled under reflux for 1 hour. After the temperature was returned to room temperature, the resulting crystals were filtered under pressure in an atmosphere of gaseous nitrogen and then washed three times simple anhydrous diethyl ether. In addition, the crystals were purified by vacuum distillation (5,0 kPa, 80°C), while receiving 1,11 g of methyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphine in the form of a transparent liquid; the yield was 54%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ and 3.16 (m, 2H), 2,68 (m, 2H), 2.63 in (d, 6N), and 2.14 (m, 1H), 1,35 (m, 1H), of 1.16 (d, 3H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 90,09 (s, 1P).

The structural formula is shown below.

Chemical formula 31

(ab) Receivingn-butylsulfide methyl-n-butyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphonium

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in ATM is the field of gaseous nitrogen was loaded 0,80 g (0,0054 mol) of methyl(N,N '-dimethyl-1,3-Propylenediamine)phosphine obtained under item (aa), cooled with ice and then added dropwise 1.1 ml (0,0054 mol) di-n-butylsulfide. After stirring the reaction mixture at 30°C for 3 days it was thrice washed simple diethyl ether. By vacuum drying at room temperature was obtained 1.0 gn-butylsulfide methyl-nbutyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphonium in the form of a yellow liquid; yield was 52%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ was 4.02 (t, 2H), 3,26 (m, 2H), 3,14 (m, 2H), 2,61 (d, 6N), of 2.50 (m, 2H), 2.13 in (d, 3H), of 1.99 (m, 2H), 1,64 (m, 2H), 1,42 (m, 6N), of 0.95 (m, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 71,32 (s, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 32

(AU) Obtaining bistrifluormethylbenzene methyl-n-butyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphonium

In a 50 ml flask with a trap to trap, equipped with a magnetic IU the Alcoy, download of 1.00 g (0,0028 mol)n-butylsulfide methyl-n-butyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphonium obtained by p.(ab), and 10 ml of ultrapure water. As stirring the reaction mixture to the reaction mixture were added an aqueous solution, in which 10 ml of ultrapure water was dissolved 0,86 g (0,0030 mol) LiTFSI, and the resulting mixture was further stirred at room temperature for 20 hours. The obtained salt was extracted with 20 ml of CH2Cl2. The aqueous layer was additionally extracted with 20 ml of CH2Cl2. The organic layer is washed three times with 20 ml of ultrapure water, and then the obtained extracted solution was concentrated with a rotary evaporator and dried in vacuum at 80°C. thus was obtained a 1.00 g of bistrifluormethylbenzene methyl-n-butyl-(N,N'-dimethyl-1,3-Propylenediamine)phosphonium in the form of a transparent liquid yellow; the yield was 76%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ up 3.22 (m, 4H), was 2.76 (d, 6N), 2,28 (m, 2H), 2,01 (m, 2H), of 1.88 (d, 3H), of 1.46 (m, 4H), of 0.97 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3one hundred is a standard substance: CF 3Cl) δ -78,79 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 69,52 (m, 1P).

The structural formula shown below (in the formula dashed line shows the coupled structure).

Chemical formula 33

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 36.2°C. the crystallization Temperature was equal to -24,6°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 285,5°C.

Example 9

(ad) Obtaining dichloro-(N-methylethylamine)axiostar

In a 1000 ml three-neck flask equipped with a dropping funnel and a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen downloaded 19 ml (0,208 mol) of phosphorylchloride and 400 ml of anhydrous simple diethyl ether and cooled the mixture to 5°C or below in a bath with ice. As stirring the reaction mixture to the reaction mixture slowly dropwise added to 18.1 ml (0,208 mol) of N-methylethylamine. In addition, dropwise added 29 ml (0,208 mol) of triethylamine. After stirring the reaction mixture for 1 hour in BP is me its cooling with ice, the reaction mixture was filtered under pressure in the atmosphere of nitrogen gas. The resulting crystals are washed three times simple anhydrous diethyl ether and then purified them by vacuum distillation (1,3 kPa, 80°C), while receiving of 2.68 g of dichloro-(N-methylethylamine)axiostar in the form of a transparent liquid; the yield was 89%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.32 (m, 2H), 2,86 (d, 3H), of 1.24 (t, 3H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 17,88 (m, 1P).

The structural formula is shown below.

Chemical formula 34

(ae) Obtaining dimethyl-(N-methylethylamine)axiostar

300 ml chetyrehosnuju flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 15,00 g (0,08500 mol) of dichloro-(N-methylethylamine)axiostar received under item (ad), and 100 ml of anhydrous simple diethyl ether and the mixture was cooled to -78°C. as stirring the reaction mixture to the reaction mixture was added dropwise 57 ml of 3 mol/l solution of CH3MgBr in a simple diethyl ether. After the lane is masiania the reaction mixture for 15 minutes, the temperature was slowly increased and then the reaction mixture is boiled under reflux for 3 hours. After the temperature was returned to room temperature, the resulting crystals were filtered under pressure in an atmosphere of gaseous nitrogen and then washed three times simple anhydrous diethyl ether. In addition, the crystals were purified by vacuum distillation (0.1 kPa, 50-55°C), while receiving 1.42 g of dimethyl-(N-methylethylamine)axiostar in the form of a transparent liquid; the yield was 12%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ to 3.02 (m, 2H), 2.63 in (d, 3H), of 1.46 (d, 6N), to 1.14 (t, 3H).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,28 (m, 1P)

The structural formula is shown below.

Chemical formula 35

(af) Receivingn-butylsulfide dimethyl-(N-methylethylamine)-n-butoxypropan

In 50 ml of dvuhgolosy flask equipped with a magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 1.42 g (0,0105 mol) of dimethyl-(N-methylethylamine)axiostar received under item(ae), and cooled with ice. Then was added dropwise 2.5 ml (0,0126 mol) di-n-butylal the ATA. The resulting reaction mixture was stirred at 30°C for 7 days and then washed three times its ordinary diethyl ether and dried in vacuum at room temperature, while receiving 2,59 g n butylsulfide dimethyl-(N-methylethylamine)-n-butoxypropan in the form of a white solid; yield was 71%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: acetone-d6standard substance: tetramethylsilane was) δ 4,24 (m, 2H), 3,84 (t, 2H), 3,34 (m, 2H), 2,96 (d, 3H), 2,32 (d, 6N), 1,73 is 1.34 (m, 8H), 1,25 (t, 3H), 0,99-0,88 (m, 6N).

31P-NMR (121 MHz, solvent: acetone-d6standard substance: triphenylphosphine) δ 80,00 (m, 1P).

The structural formula is shown below.

Chemical formula 36

(ag) Obtaining bistrifluormethylbenzene dimethyl-(N-methylethylamine)-n-butoxypropan

In a 50 ml flask with a trap to trap, equipped with a magnetic stirrer, was loaded at 2.59 g (0,0075 mol)n-butylsulfide dimethyl-(N-methylethylamine)-n-butoxypropan received under item(af). With stirring, was added an aqueous solution in which 25 ml of ultrapure water was dissolved 2.6 g (0,0090 mol) LiTSI. The resulting reaction mixture was additionally stirred at room temperature for 14 hours. The obtained salt was extracted with 50 ml of CH2Cl2and the aqueous layer was additionally extracted with 50 ml of CH2Cl2. The organic layer is washed three times with 100 ml of ultrapure water and then received ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 80°C. thus was obtained 2,94 g bistrifluormethylbenzene dimethyl-(N-methylethylamine)-n-butoxypropan in the form of a transparent liquid; the yield was 83%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 4,03 (quart, 2H), 3,29 (m, 2H), 2,85 (d, 3H), 2.05 is (d, 6N), by 1.68 (m, 2H), 1.39 in (m, 2H), of 1.23 (t, 3H), were 0.94 (t, 3H).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,99 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 76,98 (m, 1P).

The structural formula is shown below.

Chemical formula 37

The melting point was measured using differential scanning ka is erimeter (DSC8230, production company Shimadzu Corp.). The transition temperature in the glassy state was equal to -88,7°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 217,2°C.

Example 10

B(a) Obtaining hydrochloride Tris(diethylamino)phosphoamino

In a 500 ml three-neck flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 20,0 g (0,146 mol) of trichloride phosphorus and 185 ml (1,91 mol) of carbon tetrachloride and the mixture was cooled to 5°C or below in a bath with ice. Then slowly dropwise added 91,5 ml (0,884 mol) of diethylamine at 30°C and under stirring. After the temperature became constant, the reaction mixture was additionally stirred for 1 hour at room temperature, thus obtaining a yellow liquid. Then from the bottom of the liquid at 25°C was barbotirovany anhydrous ammonia for approximately 1.5 hours, thus obtaining a suspension of a pale yellow color. After ozonation, the suspension was further stirred overnight. The suspension was filtered and the obtained residue was washed with 10 ml tetrachloride in which laroda. The obtained filtrate was subjected to vacuum distillation to remove solvent. When this was received hydrochloride Tris(diethylamino)phosphoamino in the form methodoloy viscous liquid yellow color.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 9,88 (W, 1H), 3,13 (m, N), 1,17 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 41,34 (m, 1P).

The structural formula is shown below.

Chemical formula 38

B(b) Obtaining iodide Tris(diethylamino)dimethylaminopropane

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 7,26 g (approximately 0,0243 mol) of the crude hydrochloride Tris(diethylamino)phosphoamino obtained in paragraph B(a), and slowly dropwise added an aqueous solution in which 2.5 ml of ultrapure water was dissolved 2,33 g (0,0583 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 10 ml of ultrapure water was rest the Reno 2,59 g (0,0648 mol) of NaOH and 7.1 ml (to 0.011 mol) of iodomethane, and the resulting reaction solution was stirred at 70°C for 15 hours.

After the temperature was returned to room temperature, the reaction solution was extracted with 30 ml of CH2Cl2separating into two layers. The aqueous layer was additionally was twice extracted with CH2Cl2. Extract with organic layer was dried with anhydrous Na2SO4was filtered , subjected to vacuum distillation to remove most of the solvent, washed three times with simple ether and dried in vacuum at 90°C, while receiving a 9.9 g of oily product, painted in brown color (the yield was 97% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,20 (m, N), 2,87 (C, 6N), 1,25 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,12 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 39

B(c) Obtaining bistrifluormethylbenzene Tris(diethylamino)is dimetilaminoflavonola

In 10 ml of CH2Cl2dissolved 9,9 g (0,0236 mol) iodide Tris(diethylamino)dimethylaminopropane received under paragraph B(b), which then was extracted three times back with 150 ml of ultrapure water. To aqueous solutions obtained during the second and third reverse extraction, was added an aqueous solution in which 30 ml of ultrapure water was dissolved 6.8 g (0,024 mol) LiTFSI, and then the resulting mixture was stirred at room temperature for 1 hour. The obtained salt was extracted with 100 ml of CH2Cl2and the aqueous layer was additionally was twice extracted with 100 ml of CH2Cl2. After twice washing ultrapure water obtained ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 90°C, while receiving 4,55 g of the product; the yield was 34,%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,13 (m, N), 2,77 (, 6N), to 1.21 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,79 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenyl ospin) δ 41,34 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 40

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 119.8°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 359,1°C.

Example 11

B(d) Obtaining bromide tetrakis(diethylamino)phosphonium

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 7,26 g (approximately 0,0243 mol) of the crude hydrochloride Tris(diethylamino)phosphoamino obtained in paragraph B(a), and slowly dropwise added an aqueous solution in which 2.5 ml of ultrapure water was dissolved 2,33 g (0,0583 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 5 ml of ultrapure water was dissolved 1,16 g (0,0291 mol) of NaOH and 4.3 ml (0,057 mol) of brometane, and the resulting reaction solution was stirred at 70°C for 25 hours.

After the temperature was returned to room the first temperature, the reaction solution was extracted with 10 ml of CH2Cl2separating into two layers, and the aqueous layer was twice additionally was extracted with CH2Cl2. Extract with organic layer was dried with anhydrous Na2SO4was filtered , subjected to vacuum distillation to remove most of the solvent, washed three times with simple ether and dried in vacuum at 90°C, while receiving 7,18 g of oily product, painted in brown color (the yield was 71% for PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,20 (m, N), 1,25 (t, 24N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 44,03 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 41

B(e) Obtaining bistrifluormethylbenzene tetrakis(diethylamino)phosphonium

In 5 ml of CH2Cl2dissolved 13,7 g (0,0343 mol) of bromide tetrakis(diethylamino)phosphonium received under paragraph B(d), then the extras who were garofali back with 70 ml of ultrapure water. To the aqueous solution obtained during back extraction was added an aqueous solution in which 50 ml of ultrapure water was dissolved 10.0 g (0,0348 mol) LiTFSI, and then the resulting mixture was stirred at room temperature for 1 hour. The obtained salt was extracted with 70 ml of CH2Cl2and the aqueous layer was additionally extracted with 20 ml of CH2Cl2. After twice washing with 70 ml of ultrapure water obtained ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 90°C, while receiving 14,22 g of the product; the yield was 97.3% in the calculation of the PCl3.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,14 (m, N), to 1.21 (t, 24N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,80 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,96 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 42

The melting point of erali using a differential scanning calorimeter (DSC8230, production company Shimadzu Corp.). Peak, which could be considered as the melting point was not observed. By visual observation found that the melting began at 90°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 376,0°C.

Example 12

B(f) Obtaining iodide Tris(diethylamino)di-n-propylaminosulfonyl

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 10.0 g (approximately 0,0335 mol) of the crude hydrochloride Tris(diethylamino)phosphoamino obtained in paragraph B(a), and slowly dropwise added an aqueous solution in which 3 ml of ultrapure water was dissolved 2,68 g (0,0670 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 20 ml of ultrapure water was dissolved 5,51 g (was 0.138 mol) of NaOH, and 26 ml (0,238 mol) of iodine-n-propane, and the resulting reaction mixture was stirred at 70°C for 19 hours.

After the temperature was returned to room temperature, the reaction mixture was extracted with 50 ml of CH2Cl2separating into two layers, and the aqueous layer SS is niteline was extracted with CH 2Cl2. Extract with organic layer was dried with anhydrous Na2SO4was filtered , subjected to vacuum distillation to remove most of the solvent, washed three times with simple ether and dried in vacuum at 90°C, while receiving 16,47 g of brown oily product.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,19 (m, N), 2,99 (m, 4H), of 1.62 (m, 4H), of 1.23 (t, N), is 0.96 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,61 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 43

B(g) Obtaining bistrifluormethylbenzene Tris(diethylamino)di-n-propylaminosulfonyl

In 5 ml of CH2Cl2dissolved 16,47 g (0,0347 mol) iodide Tris(diethylamino)di-n-propylaminosulfonyl received under paragraph B(f), which is then five times were back extracted with 50 ml of ultrapure water. To aqueous solutions obtained in the third, fourth and FIF is Oh reverse extraction, was added an aqueous solution in which 50 ml of ultrapure water was dissolved 10.0 g (0.035 mol) LiTFSI, and then the resulting mixture was stirred at 50°C for 4 days. The obtained salt was extracted with 150 ml of CH2Cl2and the aqueous layer was additionally extracted with 50 ml of CH2Cl2. After twice washing ultrapure water obtained ekstragirovanny the solution was concentrated using a rotary evaporator and dried in vacuum at 90°C, while receiving 4.42 g of product; output 20.3% for PCl3.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,14 (m, N), 2,95 (m, 4H) to 1.60 (m, 4H), 1,22 (t, N), of 0.93 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,75 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,96 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 44

The melting point was measured using a differential scanning calorimeter is (DSC8230, production company Shimadzu Corp.). The melting point was equal 94,1°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 362,0°C.

Example 13

B(h) Obtaining iodide Tris(diethylamino)di-n-butylaminoethyl

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 42,4 g (approximately 0,142 mol) of the crude hydrochloride Tris(diethylamino)phosphoamino obtained in paragraph B(a), and slowly dropwise added an aqueous solution in which 12 ml of ultrapure water was dissolved 11,68 g (0,292 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 90 ml of ultrapure water was dissolved 23,36 g (0,586 mol) of NaOH, and 118 ml (0,238 mol) of iodine-n-butane, and the resulting reaction mixture was stirred at 70°C for 19 hours.

After the temperature was returned to room temperature, the reaction mixture separated into two layers were separated. The organic layer was washed five times with ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 70°C, more is tion washed three times simple ether, again subjected to vacuum distillation to remove most of the solvent, and dried at 70°C, while receiving 42,58 g of brown oily product (yield was 59.7% for PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,19 (m, N), to 3.02 (m, 4H) and 1.56 (m, 4H), of 1.35 (m, 4H), 1,25 (t, N), and 0.98 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,74 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 45

(I) Obtaining bistrifluormethylbenzene

Tris(diethylamino)di-n-butylaminoethyl

To 48,75 g (0,097 mol) iodide Tris(diethylamino)-di-n-butylaminoethyl received under paragraph B(h), was added an aqueous solution in which 200 ml of ultrapure water was dissolved 28,7 g (0,100 mol) LiTFSI, and then the resulting mixture was stirred at 50°C for 3 days. The obtained salt was extracted with 100 ml of CH2Cl2and the aqueous layer was additionally extracted with 50 ml of CH2 Cl2. After five times washing ultrapure water obtained ekstragirovanny the solution was concentrated using a rotary evaporator, dried in vacuum at 90°C and then passed through a column of aluminum oxide (manifesting solvent: CH2Cl2). Extracted solution was again concentrated using a rotary evaporator and dried in vacuum at 90°C, while receiving 54,59 g of the product; output amounted to 85.8%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,14 (m, N), 2,99 (m, 4H), and 1.54 (m, 4H), of 1.33 (m, 4H), 1,22 (t, N), of 0.97 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,75 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,85 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 46

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 25.4°C. Temp is the temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, production company Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 362,5°C.

Electric conductivity was measured by AC impedance method (system for electrochemical measurements HZ-3000, made by Hokuto Denko Corp.), was 0,0642 cm-1at 50°C.

Electrochemical window was in the range from minus 0.1 V to 4.8 V relative to Li/Li+, which was obtained from cyclic voltammogram measured using the system for electrochemical measurements HZ-3000 production company Hokuto Denko Corp., using a Pt working electrode and counter-electrode and Li reference electrode. The CV curve of bistrifluormethylbenzene Tris(diethylamino)di-n-butylaminoethyl shown in figure 3.

To 3.8 g (0,0058 mol) of bistrifluormethylbenzene Tris(diethylamino)di-n-butylaminoethyl was added an aqueous solution in which 20 ml of H2O was dissolved 5 g of NaOH, and then the resulting reaction mixture was stirred at 50°C for 14 hours. Then to the reaction mixture were added 50 ml of CH2Cl2and the resulting solution was divided. The organic layer is washed three times with 30 ml of ultrapure water, was concentrated in vacuum and dried in vacuum at 80°C, while receiving 3.7 g of product; the yield was 96%.

A similar experiment was performed, p is imanae bistrifluormethylbenzene ethylmethylketone; the yield was 81%.

B(j) Receiving nitrate Tris(diethylamino)di-n-butylaminoethyl

In 20 ml of CH2Cl2dissolved 2,48 g (0,00494 mol) iodide Tris(diethylamino)-di-n-butylaminoethyl received under paragraph B(h). To the resulting solution were added 20 ml of an aqueous solution in which the dissolved 0.87 g AgNO3. The obtained crystals were filtered off. The filtrate is washed twice ultrapure water, was concentrated using a rotary evaporator and dried in vacuum at 80°C, while receiving 1.47 g of product; output amounted to 67.9%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,17 (m, N), a 3.01 (m, 4H), of 1.55 (m, 4H), of 1.33 (m, 4H), 1,24 (t, N), of 0.97 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,81 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 47

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 61.2°C. it is the temperature value of thermal decomposition was measured using thermogravimetric analyzer (TG8120, production company Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 282,8°C.

Example 14

(K) Obtaining hydrochloride Tris-(N-methyl-n-butylamino)phosphoamino

In a 500 ml three-neck flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 10.0 g (0,0728 mol) of trichloride phosphorus and 92 ml (0,954 mol) of carbon tetrachloride and the mixture was cooled to 5°C or below in a bath with ice. Then, while mixing, slowly dropwise added 52 ml (0,442 mol) N-methyl-n-butylamine at 30°C or below. After the temperature became constant, the reaction mixture was additionally stirred for 1 hour at room temperature, thus obtaining a yellow liquid. Then from the bottom of the liquid at 25°C was barbotirovany anhydrous ammonia, while receiving the suspension pale yellow color. After ozonation, the suspension was further stirred overnight. The suspension was filtered and the obtained residue was washed with 10 ml of carbon tetrachloride. The obtained filtrate was subjected to vacuum distillation to remove solvent. When this was received 27,30 g of the hydrochloride Tris-(N-methyl-n-butylamino)phosphoamino in the form methodoloy viscous fluid is STI yellow color.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 9,89 (W, 1H), 2,98 (m, 6N), was 2.76 (d, N), to 1.59 (m, 6N), of 1.33 (m, 6N), were 0.94 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 41,56 (m, 1P).

The structural formula is shown below.

Chemical formula 48

B(l) Receiving iodide Tris-(N-methyl-n-butylamino)dimethylaminopropane

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded to 5.00 g (approximately 0,0134 mol) of the crude hydrochloride Tris-(N-methyl-nbutylamino)phosphoamino received under paragraph B(k), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved 1.07 g (0,0268 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 10 ml of ultrapure water was dissolved 2,68 g (0,067 mol) of NaOH and 6 ml (0.09 mol) of iodomethane and the resulting reaction mixture was stirred at 70°C for 3.5 hours.

After the temperature of the return which was amalas to room temperature, added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving of 4.75 g of a brown oily product (yield amounted to 74.7% for PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,96 (m, 6N), 2,84 (l, 15 NM), to 1.59 (m, 6N), of 1.34 (m, 6N), of 0.97 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 42,89 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 49

B(m) Obtaining bistrifluormethylbenzene

Tris-(N-methyl-nbutylamino)dimethylaminopropane

To 4,75 g (0,010 mol) iodide Tris-(N-methyl-n-butylamino)DIMET aminophosphine, received by PV(l), was added an aqueous solution in which 50 ml of ultrapure water was dissolved 3.2 g (to 0.011 mol) LiTFSI, and the resulting solution was stirred at 50°C for 19 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 5.35 g of product; output accounted for 87.2%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,90 (m, 6N), was 2.76 (d, N), is 2.74 (d, 6N), of 1.57 (m, 6N), 1,32 (m, 6N), is 0.96 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,84 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,85 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 50

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). Peak, which could be considered as t is CCW melting it was not observed. At room temperature 20°C visual connection was in the form of a liquid. The temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 395,0°C.

Example 15

B(n) Obtaining iodide Tris-(N-methyl-n-butylamino)diethylaminopentane

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 5.53 g (approximately 0,0147 mol) of the crude hydrochloride Tris-(N-methyl-n-butylamino)phosphoamino received under paragraph B(k), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved 1.18 g (0,0295 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 10 ml of ultrapure water was dissolved 2,95 g (0,0737 mol) NaOH and 8.5 ml (0.10 mol) of iodomethane and the resulting reaction mixture was stirred at 70°C for 15,5 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distill the tion to remove most of the solvent, was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 5,41 g of brown oily product (yield was 75.3% in the calculation of the PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ and 3.16 (m, 4H), of 2.97 (m, 6N), 2,84 (d, N), to 1.59 (m, 6N), of 1.34 (m, 6N), 1,25 (t, 6N), of 0.97 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,26 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 51

B(o) Obtaining bistrifluormethylbenzene Tris-(N-methyl-nbutylamino)diethylaminopentane

To 5,41 g (to 0.011 mol) iodide Tris-(N-methyl-n-butylamino)dimethylaminopropane received under paragraph B(n), was added an aqueous solution in which 50 ml of ultrapure water was dissolved 3.5 g (0.012 mol) LiTFSI, and the resulting solution was stirred at 50°C for 23 hours. The obtained Sol e who was strayaway 100 ml of CH 2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving to 6.43 g of the product; output amounted to 90.3%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10 (m, 4H), 2.91 in (m, 6N), was 2.76 (d, N), of 1.57 (m, 6N), of 1.33 (m, 6N), 1,22 (t, 6N), is 0.96 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,82 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,44 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 52

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was 3.7°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 1°C/min, equal 402,1°C.

Example 16

B(p) Obtaining iodide Tris-(N-methyl-nbutylamino)di-n-propylaminosulfonyl

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 0,90 g (approximately 0,0025 mol) of the crude hydrochloride Tris-(N-methyl-nbutylamino)phosphoamino received under paragraph B(k), and slowly dropwise added an aqueous solution in which 0.5 ml of ultrapure water was dissolved 0.20 g (0,0050 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 2 ml of ultrapure water was dissolved 0.50 g (of 0.0125 mol) of NaOH, and 1.70 ml (0,0175 mol) of iodine-n-propane and the resulting reaction mixture was stirred at 70°C for 15,5 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 0,93 g of iodide Tris-(N-methyl-n-butylamino)di-npropylamino Estonia (the yield was 76% for PCl 3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,96 (m, 10H), and 2.83 (d, N), to 1.60 (m, 10H), 1,25 (m, 6N), of 0.97 (m, 15 NM).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,13 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 53

B(q) Obtaining bistrifluormethylbenzene Tris-(N-methyl-nbutylamino)di-n-propylaminosulfonyl

To 0,93 g (0,0018 mol) iodide Tris-(N-methyl-n-butylamino)di-n-propylaminosulfonyl received under paragraph B(p), was added an aqueous solution in which 15 ml of ultrapure water was dissolved 0.6 g (0.002 mol) LiTFSI, and the resulting solution was stirred at 50°C for 39 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 0.52 g of bistrifluormethylbenzene Tris-(N-methyl-n-butylamino)di-n-propylaminosulfonyl; Ihad was 43%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2.91 in (m, 10H), 2,75 (d, N), was 1.58 (m, 10H), of 1.33 (m, 6N), of 0.95 (m, 15 NM).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,76 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,27 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 54

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -71,4°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 386,7°C.

Example 17

B(r) Receiving iodide Tris-(N-methyl-n-butylamino)di-n-butylaminoethyl

In a 100 ml three-neck flask equipped with a reflux is m and a magnetic stirrer, downloaded from 0.90 g (approximately 0,0025 mol) of the crude hydrochloride Tris-(N-methyl-n-butylamino)phosphoamino received under paragraph B(k), and slowly dropwise added an aqueous solution in which 0.5 ml of ultrapure water was dissolved 0.20 g (0,0050 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 2 ml of ultrapure water was dissolved 0.50 g (of 0.0125 mol) of NaOH, and of 2.05 ml (0,0175 mol) of iodine-n-butane and the resulting reaction mixture was stirred at 70°C for 15,5 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving of 1.05 g of the iodide of Tris-(N-methyl-n-butylamino)di-n-butylaminoethyl (the yield was 76% for PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, producing the TBA BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 2,98 (m, 10H), and 2.83 (d, N), was 1.58 (m, 10H), of 1.35 (m, 10H), of 0.93 (t, 15 NM).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,22 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 55

B(s) Receiving bistrifluormethylbenzene Tris-(N-methyl-n-butylamino)di-n-butylaminoethyl

To 1.05 g (0,0019 mol) iodide Tris-(N-methyl-n-butylamino)di-n-propylaminosulfonyl received under paragraph B(r), was added an aqueous solution in which 15 ml of ultrapure water was dissolved 0.6 g (0.002 mol) LiTFSI, and the resulting solution was stirred at 50°C for 39 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 0,41 g bistrifluormethylbenzene Tris-(N-methyl-n-butylamino)di-n-butylaminoethyl; output amounted to 31%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, the production company who BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ equal to 2.94 (m, 10H), 2,75 (d, N), of 1.55 (m, 10H), of 1.33 (m, 10H), of 0.97 (t, 15 NM).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,77 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,44 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 56

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -70,5°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 387,2°C.

Example 18

B(t) Obtaining bromide Tris-(N-methyl-n-butylamino)dimethoxyacetophenone

In a 100 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 0,90 g (approximately 0,0025 mol) of the crude hydrochloride Tris-(N-methyl-n-butylamino)phosphoamino received under paragraph B(k), and slowly drop is added an aqueous solution, in which 0.5 ml of ultrapure water was dissolved 0.20 g (0,0050 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 2 ml of ultrapure water was dissolved 0.50 g (of 0.0125 mol) of NaOH, and 1.67 ml (0,0175 mol) of 2-methoxyethylamine and the resulting reaction mixture was stirred at 70°C for 15,5 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 0,78 g of bromide Tris-(N-methyl-n-butylamino)dimethoxyacetophenone (the yield was 56% for PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,62 (t, 4H), 3,36 (who, 6N), of 3.32 (m, 4H), 2,98 (m, 6N), 2,82 (d, N), of 1.57 (m, 6N), to 1.31 (m, 6N), is 0.96 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 44,16 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 57

B(u) Obtaining bistrifluormethylbenzene Tris-(N-methyl-n-butylamino)dimethoxyacetophenone

To 0,78 g (0,0013 mol) of bromide Tris-(N-methyl-n-butylamino)dimethoxyacetophenone received under paragraph B(t), was added an aqueous solution in which 15 ml of ultrapure water was dissolved 0.6 g (0.002 mol) LiTFSI, and the resulting solution was stirred at 50°C for 39 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 0,93 g bistrifluormethylbenzene Tris-(N-methyl-n-butylamino)dimethoxyacetophenone; the yield was 99%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetr methylsilane) δ 3,55 (t, 4H), 3,34 (C, 6N), 3,24 (m, 4H), of 2.93 (m, 6N), a 2.75 (d, N), of 1.55 (m, 6N), 1,32 (m, 6N), is 0.96 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,76 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 44,28 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 58

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 20.8°C. the transition Temperature in the glassy state amounted to 68.1°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 396,1°C.

Example 19

B(v) Obtaining hydrochloride Tris-(N-methylethylamine)phosphoamino

In a 500 ml three-neck flask, equipped with reflux condenser, addition funnel and magnetic stirrer, at room temperature in an atmosphere of gaseous nitrogen was loaded 10.0 g (0,0728 mol) of trichloride phosphorus and 92 ml (0,954 mol) of carbon tetrachloride and cooled to 5°C or below in a bath with ice. Then, while mixing, slowly was added dropwise 7 ml (0,420 mol) of N-methylethylamine at a temperature below 30°C. After the temperature became constant, the reaction mixture was additionally stirred for 1 hour at room temperature, thus obtaining a yellow liquid. Then from the bottom of the liquid at 25°C was barbotirovany anhydrous ammonia for approximately 1.5 hours, thus obtaining a suspension of a pale yellow color. After ozonation, the suspension was further stirred overnight. The suspension was filtered and the obtained residue was washed with 10 ml of carbon tetrachloride. The obtained filtrate was subjected to vacuum distillation to remove solvent. When this was received 19,76 g of the hydrochloride Tris-(N-methylethylamine)phosphoamino in the form methodoloy viscous liquid yellow color.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ to 9.93 (width, 1H), 3,11 (m, 6N), a 2.75 (d, N), 1,20 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 41,21 (m, 1P).

The structural formula is shown below.

Chemical formula 59

B(w) Obtaining iodide Tris-(N-methylation the but)dimethylaminopropane

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 3,23 g (0,0126 mol) of the crude hydrochloride Tris-(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved 1.01 g (0,0252 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 10 ml of ultrapure water was dissolved 2,52 g (0,0629 mol) of NaOH, and 5,44 ml (0,0881 mol) of iodomethane and the resulting reaction mixture was stirred at 70°C for 4 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving of 3.27 g of iodide Tris-(N-methylethylamine)dimethylaminopropane (the yield was 73% (based on PCl3).

The compound obtained was identified using the analyzer on the basis of the nuclear magnetic resonance spectrum of the meter BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,18-of 3.07 (m, 6N), 2,85 (d-d, 15 NM), 1,25 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 42,69 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 60

B(x) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)dimethylaminopropane

To of 3.27 g (0,0087 mol) iodide Tris-(N-methylethylamine)dimethylaminopropane received under paragraph B(w), was added an aqueous solution in which 100 ml of ultrapure water was dissolved 2.8 g (0,0096 mol) LiTFSI, and the resulting solution was stirred at 50°C for 87,5 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving to 3.92 g of bistrifluormethylbenzene Tris-(N-methylethylamine)dimethylaminopropane; the yield was 85%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). Received the special the Central data below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,09-2,99 (m, 6N), 2,75 (d-d, 15 NM), 1,22 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,83 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 42,86 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 61

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal uniforms, 127.6°C. the crystallization Temperature was equal to 123,3°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 411,4°C.

B(y) Obtaining iodide Tris-(N-methylethylamine)diethylaminopentane

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 3,10 g (0,0121 mol) of the crude hydrochloride Tris-(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved 0.96 g (0,0241 mol) of NaOH. After 1 hour p is remesiana at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution, in which 10 ml of ultrapure water was dissolved 2,42 g (0,0604 mol) of NaOH, and 6.8 ml (0,0845 mol) of itatani, and the resulting reaction mixture was stirred at 70°C for 20 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 3.33 g of iodide Tris-(N-methylethylamine)diethylaminopentane (the yield was 72% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,21-is 3.08 (m, 10H), 2,84 (d, N), 1,25 (t, 15 NM).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,02 (m, 1P).

The structural formula shown below (in the formula, the system, the IRNA lines shown coupled structure).

Chemical formula 62

B(z) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)diethylaminopentane

To 3.33 g (0,00824 mol) iodide Tris-(N-methylethylamine)diethylaminopentane received under paragraph B(y), was added an aqueous solution in which 100 ml of ultrapure water was dissolved 2.6 g (0,0091 mol) LiTFSI, and the resulting solution was stirred at 50°C for 87,5 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving of 3.77 g of bistrifluormethylbenzene Tris-(N-methylethylamine)diethylaminopentane; the yield was 82%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,17-2,99 (m, 10H), 2,75 (d, N), 1,22 (t, 15 NM).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,85 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,11 (m, 1P).

The structural formula shown below (in the formula dotted l the values shown coupled structure).

Chemical formula 63

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point equaled by 115.7°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 408,7°C.

B(aa) Receive iodide Tris-(N-methylethylamine)di-npropylaminosulfonyl

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 2,00 g (0,00779 mol) of the crude hydrochloride Tris-(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved and 0.62 g (0,00156 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 6 ml of ultrapure water was dissolved 1.56 g (0,0389 mol) of NaOH, and 5.3 ml (by 0.055 mol) of iodine-n-propane and the resulting reaction mixture was stirred at 70°C for 15 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. A dedicated PR is anceschi the five-layer washed with ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 2,47 g of iodide Tris-(N-methylethylamine)di-n-propylaminoethyl (yield: 78% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,18-is 3.08 (m, 6N), 3,02 of 2.92 (m, 4H), and 2.83 (d, N), 1,67-to 1.59 (m, 4H), 1,25 (t, N), is 0.96 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 42,91 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 64

B(ab) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)di-npropylaminosulfonyl

To 2,47 g (0,00571 mol) iodide Tris-(N-methylethylamine)di-n-propylaminosulfonyl received under paragraph B(aa), was added an aqueous solution in which 100 ml of ultrapure water was dissolved 1.8 g (0,0063 mol) LiTFSI, and p the obtained solution was stirred at 50°C for 18 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 2,53 g bistrifluormethylbenzene Tris-(N-methylethylamine)di-npropylaminosulfonyl; the yield was 76%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10-2,99 (m, 6N), 2,97-2,89 (m, 4H), to 2.74 (d, N), 1,64-of 1.56 (m, 4H), 1,22 (t, N), of 0.93 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,88 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 42,97 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 65

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.) Peak, which could be considered as the melting point was not observed. The temperature of thermal decomposition was measured with those who moralisations analyzer (TG8120, production company Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 402,8°C.

B(ac) Receiving iodide Tris-(N-methylethylamine)di-n-butylaminoethyl

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded to 2.06 g (0,00802 mol) of the hydrochloride of the crude Tris(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added an aqueous solution in which 1 ml of ultrapure water was dissolved 0.64 g (0,0160 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 6 ml of ultrapure water was dissolved 1,60 g (0,0401 mol) of NaOH and 6.5 ml (0,056 mol) of iodine-n-butane and the resulting reaction mixture was stirred at 70°C for 15 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer is washed five times ultrapure water, was subjected to vacuum distillation to remove most of the solvent was dried in vacuum at 80°C, optionally washed three times simple ether was again subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, olucha this 2,72 g of iodide Tris-(N-methylethylamine)di- nbutylaminoethyl (yield 78% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,19-is 3.08 (m, 6N), 3,05-2,96 (m, 4H), and 2.83 (d, N), and 1.56 (m, 4H), 1,39 to 1.31 (m, 4H), 1,25 (t, N), of 0.97 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,02 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 66

B (ad) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)di-nbutylaminoethyl

To 2,72 g (0,00590 mol) iodide Tris-(N-methylethylamine)di-n-butylaminoethyl received under paragraph B(ac), was added an aqueous solution in which 100 ml of ultrapure water was dissolved 1.9 g (0,0066 mol) LiTFSI, and the resulting solution was stirred at 50°C for 18 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 2,56 g bistrifluormethylbenzene Tr is s-(N-methylethylamine)di- n-butylaminoethyl; the yield was 71%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10-only 2.91 (m, 10H), is 2.74 (d, N), of 1.55 (m, 4H), 1,36-of 1.29 (m, 4H), to 1.21 (t, N), is 0.96 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,86 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,06 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 67

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 20, 8C°C. the transition Temperature in the glassy state was equal to 83.7°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 406,0°C.

B(ae) Receive thriftimart Tris-(N-methylethylamine)di-nthe butyl is Novotny

To 1.00 g (0,00217 mol) iodide Tris-(N-methylethylamine)di-nbutylaminoethyl received under paragraph B(ac), was added an aqueous solution in which 2 ml of 1 wt.% aqueous solution of NaOH was dissolved 0.3 g (0,0026 mol) NaBF4and the resulting solution was stirred at 60°C for 2 hours. After removing the resulting aqueous layer of the reaction mixture was washed with 2 ml of 1 wt.% aqueous NaOH solution and 2 ml of ultrapure water and then dried in vacuum at 80°C, while receiving 0,23 g thriftimart Tris-(N-methylethylamine)di-nbutylaminoethyl; output was 25%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ is 3.08 (m, 6N), 2,98 (m, 4H), 2,78 (d, N), and 1.56 (m, 4H), of 1.34 (m, 4H), of 1.23 (t, N), is 0.96 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -153,52 (d, 4F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,24 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 68

The melting point was measured using differe the social scanning calorimeter (DSC8230, production company Shimadzu Corp.). The transition temperature in the glassy state was equal to -61,6°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 309,2°C.

B(af) Receiving hexaphosphate Tris-(N-methylethylamine)di-nbutylaminoethyl

To 1.00 g (0,00217 mol) iodide Tris-(N-methylethylamine)di-n-butylaminoethyl received under paragraph B(ac), was added an aqueous solution in which 5 ml of ultrapure water were dissolved 0.40 g (0,0026 mol) LiPF6and the resulting solution was stirred at room temperature for 20 hours. The obtained salt was extracted with 10 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator and dried in vacuum at 80°C, while receiving 0.97 g of hexaflurophosphate Tris-(N-methylethylamine)di-n-butylaminoethyl; the yield was 93%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3, standard vases is in: tetramethylsilane was) δ 3,05 (m, 6N), of 2.97 (m, 4H), 2,75 (d, N), of 1.55 (m, 4H), of 1.33 (m, 4H), 1,22 (t, N), is 0.96 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -73,27 (d, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,26 (m, 1P), -144,30 (cept, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 69

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -61,7°C the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 296,5°C.

B(ag) Receive dicyanamide Tris-(N-methylethylamine)di-n-butylaminoethyl

In 5 ml of ultrapure water was dissolved and 0.46 g (0,0010 mol) iodide Tris-(N-methylethylamine)di-n-butylaminoethyl received under paragraph B(ac), and was added 0.21 g (0,0012 mol) AgN(CN)2, which was obtained from silver nitrate and NaN(CN)2. Then the resulting reaction mixture was stirred at room temperature for 20 hours. After adding to the reaction mixture 10 ml of dihormati is and the reaction mixture was stirred for some time, the obtained crystals were filtered in order to allocate the resulting aqueous layer. Thanks to a threefold washing ultrapure water concentration in vacuo using a rotary evaporator and vacuum-dried at 80°C was obtained 0.27 g of dicyanamide Tris-(N-methylethylamine)di-nbutylaminoethyl; the yield was 68%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,15-2,96 (m, 10H), 2,80 (d, N), was 1.58 (m, 4H), of 1.36 (m, 4h), of 1.23 (t, N), and 0.98 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,17 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 70

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -66,8°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding to loss the weight 5%, the measured rate of temperature increase of 10°C/min, was 270,8°C.

B(ah) Obtaining iodide Tris-(N-methylethylamine)di-n-intraministerial

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded 1.01 g (approximately to 0.0039 mol) of the crude hydrochloride Tris-(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added an aqueous solution in which 0.5 ml of ultrapure water was dissolved 0,314 g (0,00787 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 3 ml of ultrapure water was dissolved 0,79 g (0,0197 mol) of NaOH, and 3.1 ml (0,028 mol) of identne and the resulting reaction mixture was stirred at 70°C for 6 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer washed three times ultrapure water, was subjected to vacuum distillation to remove most of the solvent and dried in vacuum at 80°C, while receiving 1,58 g of iodide Tris-(N-methylethylamine)di-n-intraministerial (yield: 82% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.12 (m, 6N), 2,99 (m, 4H), 2,82 (d, N), of 1.57 (m, 4H), 1,42 is 1.23 (m, 17H), to 0.92 (t, 6N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,00 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 71

B(ai) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)di-n-intraministerial

To 0.95 g (0,0019 mol) iodide Tris-(N-methylethylamine)di-n-intraministerial received under paragraph B(ah), was added an aqueous solution in which 5 ml of ultrapure water was dissolved 0.9 g (0,0021 mol) LiTFSI, and the resulting solution was stirred at room temperature for 18 hours. The obtained salt was extracted with 10 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 0,94 g bistrifluormethylbenzene Tris-(N-methylethylamine)di-n-intraministerial; the yield was 75%.

The compound obtained was identified using the analyzer on the basis of nuclear magnetic resonance (BRUKER spectrometer Ultra Shild 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ 3,10-to 2.94 (m, 10H), and 2.79 (d, N), and 1.56 (m, 4H), 1,40-1,19 (m, 17H), to 0.92 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,81.

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,18 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 72

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -78,8°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 366,5°C.

B(aj) Obtaining bromide Tris-(N-methylethylamine)dimethoxyacetophenone

In a 50 ml three-neck flask, equipped with reflux condenser and magnetic stirrer, was loaded to 2.06 g (0,0082 mol) of the crude hydrochloride Tris-(N-methylethylamine)phosphoamino received under paragraph B(v), and slowly dropwise added to the solution meets, in which 1 ml of ultrapure water was dissolved 0.64 g (to 0.016 mol) of NaOH. After 1 hour stirring at room temperature was obtained suspension, painted in orange color. Then added an aqueous solution in which 5 ml of ultrapure water was dissolved 1,60 g (0,0401 mol) of NaOH, and 5.3 ml (0,058 mol) of 2-methoxyethylamine and the resulting reaction mixture was stirred at 70°C for 18 hours.

After the temperature was returned to room temperature, was added 50 ml of CH2Cl2in order to extract the reaction mixture. Selected organic layer washed three times ultrapure water, was subjected to vacuum distillation to remove most of the solvent, washed three times with simple ether and dried in vacuum at 80°C, while receiving of 1.97 g of bromide Tris-(N-methylethylamine)dimethoxyacetophenone (yield: 62% (based on PCl3).

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.60 (t, 4H), 3,36-3,30 (m, 10H), 3,15-3,10 (m, 6N), of 2.81 (d, N), 1,22 (t, N).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,99 (m, 1P).

Structure the RNA formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 73

In(AK) Obtaining bistrifluormethylbenzene Tris-(N-methylethylamine)dimethoxyacetophenone

To 1,97 g (0,00472 mol) of bromide Tris-(N-methylethylamine)dimethoxyacetophenone received under paragraph B(aj), was added an aqueous solution in which 50 ml of ultrapure water was dissolved 1.5 g (0,0052 mol) LiTFSI, and the resulting solution was stirred at 50°C for 64 hours. The obtained salt was extracted with 100 ml of CH2Cl2and three times washed with ultrapure water. Extracted solution was concentrated with a rotary evaporator, dried in vacuum at 80°C, while receiving 1,36 g bistrifluormethylbenzene Tris-(N-methylethylamine)dimethoxyacetophenone; the yield was 47%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.54 (t, J = 4.8 Hz, 4H), 3,34 (C, 6N), or 3.28 3.21-in (m, 4H), 3,11-a 3.01 (m, 6N), is 2.74 (d, N), 1,20 (t, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,86 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 44,06 (m, 1P).

<> The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 74

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal to -76,7°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 382,9°C.

B(am) Getting bistrifluormethylbenzene bis-(N,N'-dimethylethylenediamine)phosphonium

In a stream of nitrogen gas was downloaded 3.00 g (19,7 mmol) chloro-(N,N'-dimethylethylenediamine)phosphine obtained under item (m), and 50 ml of CCl4dried with CaCl2. At 0°C was sequentially added dropwise 2,12 ml (19,7 mmol) N,N'-dimethylethylenediamine and 2.75 ml (19,7 mmol) of triethylamine. The resulting reaction mixture was stirred at room temperature for 20 hours. Then the reaction mixture was dissolved in CH2Cl2and the resulting solution was filtered to remove the crystals. By concentration using a rotary evaporator got to 4.01 g of a viscous solid brown color. After the races the of its solids in water and washing with CH 2Cl2to remove impurities, to the obtained aqueous solution was added an aqueous solution, in which 10 ml of ultrapure water was dissolved 5.7 g (19,7 mmol) LiTFSI. The resulting solution was stirred at room temperature for four days and then was extracted twice with 30 ml of CH2Cl2. The organic phase is washed three times with 50 ml of ultrapure water. By concentration using a rotary evaporator, triple rinsing simple diethyl ether, vacuum drying and recrystallization from CH2Cl2/Et2About received 0,79 g bistrifluormethylbenzene bis-(N,N'-dimethylethylenediamine)phosphonium in the form of a white solid; yield was 8%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ is 3.41 (d, 8H), 2,68 (d, N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -78,87 (s, 6F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,58 (m, 1P).

The structural formula shown below (in the formula dotted lines shown coupled the structure).

Chemical formula 75

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The melting point was equal to 153,4°C. the crystallization Temperature was equal to 133,95°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, was 403,8°C.

B(an) Obtaining heptafluorobutyrate Tris-(N-methylethylamine)di-nintraministerial

In 50 ml of ultrapure water was dissolved 0,48 g (0,0010 mol) iodide Tris-(N-methylethylamine)di-nintraministerial received under paragraph B(ah), and was added 0.32 g (0,0010 mol) of heptafluorobutyrate silver. The resulting reaction mixture was stirred at room temperature for 1 hour. After the solvent drove by rotary evaporator, was added 30 ml of chloroform, and the obtained solid substance was besieged by using a centrifugal separator (centrifuge)to obtain the supernatant solution. By concentration in vacuo using a rotary evaporator, three times washing with 2 ml of ultrapure water and vacuum-dried at 50°C was obtained 0,49 g heptafluorobutyrate Tris-(N-methylethylamine)di-n-pentylamine stone; the yield was 87%.

The compound obtained was identified using the analyzer-based nuclear magnetic resonance spectrometer BRUKER Ultra Shield 300 NMR Spectrometer, BRUKER Limited.). The obtained spectral data are given below.

1H-NMR (300 MHz, solvent: CDCl3standard substance: tetramethylsilane was) δ of 3.07 (m, 6N), 2,96 (m, 4H), 2,77 (d, N), and 1.56 (m, 4H), 1,39-1,20 (m, 17H), to 0.92 (t, 6N).

19F-NMR (282 MHz, solvent: CDCl3standard substance: CF3Cl) δ -80,71 (t, 3F), -116,58 (kV, 2F), -126,52 (s, 2F).

31P-NMR (121 MHz, solvent: CDCl3standard substance: triphenylphosphine) δ 43,18 (m, 1P).

The structural formula shown below (in the formula, the dotted lines show the coupled structure).

Chemical formula 76

The melting point measured using a differential scanning calorimeter (DSC8230, made by Shimadzu Corp.). The transition temperature in the glassy state was equal was 72.9°C. the Temperature of thermal decomposition was measured using thermogravimetric analyzer (TG8120, made by Rigaku Corp.). The temperature corresponding weight loss of 5%, measured at a rate of temperature increase of 10°C/min, equal to 146.2°C.

As mentioned above, the results show that salt in examples stable in the liquid state is in a wide temperature range from

-20°C to about 400°C.

The field of industrial applications

The present invention offers the ionic liquid, which is stable in the liquid state in a wide temperature range and has excellent electrochemical stability.

The ionic liquid of the present invention can be applied to applications such as lithium ion batteries, capacitors, electric double layer (edlcs), fuel cells, solar cells based on sensitized dyes, electrolytes, electrolytic solutions or additives for devices, accumulating electric energy, solvents for the implementation of the reaction or separation and extraction, sensors, plating, polymers, plasticizers, lubricants and drivers.

1. The ionic liquid containing a cationic component and an anionic
component;
the cationic component is one or more kinds selected from the group of cationic components, represented by the following General formula (1):

in the above formula, the substituents R1-R11independently from each other may be the same or different from each other, and each of them is any element selected from a hydrogen atom, a C1-C30-Alki Inoi group with a linear or branched chain, With2-C30-alkenylphenol group with a linear or branched chain, containing one or more double bonds, With2-C30-alkenylphenol group with a linear or branched chain, containing one or more triple relations, cycloalkyl group, cycloalkenyl group, cycloalkenyl group, aryl group and heterocyclic group;
the hydrogen atom contained in one or more of the substituents R1-R11may be partly or completely replaced by halogen atom or partially replaced by a CN group or NO2group;
any Deputy of the substituents R1-R11together with another Deputy may form a ring structure;
the carbon atom contained in the substituents R1-R11may be replaced by atoms and/or group of atoms selected from the group consisting of-O-,
-Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NH-, -NR'-, -PR'-,
-P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O - and-P(R')2=N-, in which R' represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, cycloalkyl group, cycloalkenyl group, cycloalkenyl group, unsubstituted or substituted phenyl group, or unsubstituted or substituted heterocycle;
X1 X2and X3independent from each other and represent a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom;
two of X1X2and X3at the same time may not represent a nitrogen atom;
R3, R8or R11is a Deputy, which is present in the formula, only when X1X2or X3represents a carbon atom;
when X1represents a carbon atom, X1, R1, R2and R3together may form a saturated or partially or fully unsaturated ring structure; when X2represents a carbon atom, X2, R6, R7and R8together may form a saturated or partially or fully unsaturated ring structure; and
when X3represents a carbon atom, X3, R9, R10and R11together may form a saturated or partially or fully unsaturated ring structure;
R2, R7or R10is a Deputy, which is present in the formula, only when X1X2or X3represents a nitrogen atom or a carbon atom;
when X1represents a nitrogen atom or a carbon atom, X1, R1and R2compatible with the but each other may form a saturated or partially or fully unsaturated ring structure;
when X2represents a nitrogen atom or a carbon atom, X2, R6and R7together may form a saturated or partially or fully unsaturated ring structure; and
when X3represents a nitrogen atom or a carbon atom, X3, R9and R10together may form a saturated or partially or fully unsaturated ring structure;
the dotted lines show the coupled structure, and
anionic component is one or more kinds selected from the group consisting of [PSO3]-, [PfSO3]-, [(RfSO2)2N]-, [(RfSO2)3C]-, [(FSO2)3C]-, [ROSO3]-, [RC(O)O]-[RfC(O)O]-, [CCl3C(O)O]-, [(CN)3S]-, [(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-and I-and the anion of the formula

in the above formulae, the substituent R represents the nd any element, selected from a hydrogen atom, halogen atom, With1-C10is an alkyl group with a linear or branched chain, With2-C10-alkenylphenol group with a linear or branched chain, containing one or more double bonds, With2-C10-alkenylphenol group with a linear or branched chain, containing one or more triple relations, cycloalkyl group, cycloalkenyl group, and cycloalkenyl group;
the hydrogen atom contained in the substituent R may be partially or fully substituted by halogen atom or partially replaced by a CN group or NO2group;
the carbon atom contained in the substituent R may be replaced by atoms and/or group of atoms selected from the group consisting of-O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -SO2-, -SO3-, -N=, -N=N-, -NR'-, -N(R')2-, -PR'-, -P(O)R'-, -P(O)R'-O-, -O-P(O)R'-O - and-P(R')2=N-, in which R' represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, cycloalkyl group, cycloalkenyl group, cycloalkenyl group, unsubstituted or substituted phenyl group or unsubstituted or substituted heterocycle; and Rf represents a fluorinated Deputy.

2. The ionic liquid according to claim 1, in which the anionic component is Soboh the one or more types, selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, RfCOO-PF6-BF4-, [RfBF3]-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-and I-.

3. The ionic liquid according to claim 1, in which the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, RfCOO-PF6-BF4-, [RfBF3]-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-and NO3-.

4. The ionic liquid according to any one of claims 1 to 3, in which the substituents R1-R11in the General formula (1) represents a C1-C30is an alkyl group with a linear or branched chain, cycloalkyl group, cycloalkenyl group, cycloalkenyl group, aryl group or heterocyclic group;
the hydrogen atom contained in one or more Vice
R1-R11may be partly or completely replaced by halogen atom or partially replaced by a CN group or NO2group; and
the carbon atom contained in the substituents R1-R11may be replaced by atoms and/or group of atoms selected from the group consisting is she from-O-, -Si(R')2-, -C(O)-, -C(O)O-, -S-, -S(O) -, and-NR'-where R' represents a C1-C10is an alkyl group with a linear or branched chain alkyl group that is partially or completely replaced by fluorine atoms, cycloalkyl group, cycloalkenyl group, cycloalkenyl group, unsubstituted or substituted phenyl group or unsubstituted or substituted heterocycle.

5. The ionic liquid according to any one of claims 1 to 3, in which each of the substituents R1-R11in the General formula (1), which are the same or different from each other, represents a C1-C30is an alkyl or alkoxy group with a linear or branched chain.

6. The ionic liquid according to any one of claims 1 to 3, in which the cation in the General formula (1) has low symmetry.

7. The ionic liquid according to claim 6, in which at least one Deputy from R1-R11in the General formula (1) is a group that is different from the other.

8. The ionic liquid according to claim 7, in which at least one Deputy from R1-R11in the General formula (1) represents a C4-C20is an alkyl or alkoxy group with a linear or branched chain, and the remainder of Rnrepresent a hydrogen atom or a C1-C4is an alkyl group with a linear or branched chain.

9. The ionic liquid according to claim 7, in which, IU the greater extent, one Deputy from R1-R11in the General formula (1) contains a silyl group.

10. The ionic liquid according to claim 7, in which any of the substituents R1-R11in the General formula (1) together with another Deputy, forms a ring structure.

11. The ionic liquid according to claim 1, in which the anionic component is one or more kinds selected from the group consisting of [RfSO3]-, [(RfSO2)2N]-, RfCOO-PF6-BF4-, [RfBF3]-, [B(OR)4]-, [N(CN)2]-, [AlCl4]-, SO42-, HSO4-, NO3-and I-; a R1-R11in the General formula (1) are the same or different from each other and represent a1-C10is an alkyl or alkoxy group with a linear or branched chain.

12. The ionic liquid according to claim 1, in which at least one of R1-R11in the General formula (1) represents a C4-C20is an alkyl or alkoxy group with a linear or branched chain, and the remaining Rnrepresent a hydrogen atom or a C1-C4is an alkyl group with a linear or branched chain; and the anionic component is any of (CF3SO2)2N-PF6-and BF4-.

13. The ionic liquid according to claim 1, the which, at least one of R1-R11in the General formula (1) contains a silyl group; and the anionic component is any of (CF3SO2)2N-PF6-and BF4-.

14. The ionic liquid according to claim 1, in which each of R1-R11in the formula (1) forms a ring structure together with another Deputy; and the anionic component is any of (CF3SO2)2N-PF6-and BF4-.



 

Same patents:

Multilayer coating // 2404488

FIELD: electricity.

SUBSTANCE: multilayer coating is intended for protection of metals and alloys against oxidation at high temperatures may be used as coating for application on connecting materials in hard-oxide electrolytic devices, including hard-oxide fuel elements (HOFE) and hard-oxide electrolytic cells (HOEC). Multilayer ceramic coating contains at least two layers, at the same time the first layer (3), contacting with metal-containing surface, contains oxide with structure of perovskite or fluorite, and the second layer (4) contains oxide with structure of spinel, mine salt, corundum or wurtzite, and contacts with environment. At the same time the specified first layer (3) is characterised by value of diffusion coefficient of marked cations Mm+ of alloy, and specified second layer (4) is characterised by value of diffusion coefficient of marked oxygen ions O2-. Besides the first and/or second layer are electroconductive.

EFFECT: improved wear resistance and heat resistance of connection materials included in hard-oxide fuel elements in oxidation-recovery environment.

30 cl, 1 dwg, 12 ex

FIELD: power engineering.

SUBSTANCE: tubular electrochemical reactor comprises a porous metal bearing tube (19), coated from inside by porous first electrode (21), and this first electrode is coated from inside by dense electrolyte (23). Dense electrolyte (23) is coated from inside by the second electrode (25). Besides this second electrode provides for a tubular inner surface. Tubular current collector (27) in the form of helical spring is arranged concentrically inside the second electrode (25) and in electric contact along tangent with tubular inner surface. Helical spring has module of elasticity between 6890 MPa and 344500 MPa, diametre in its normal condition per 1.016-2.032 cm is more than diametre of inner surface, and number of turns per cm (pitch) - from 0.39 to 13.78 per cm.

EFFECT: improved operational characteristics of tubular hard-oxide fuel element.

9 cl, 1 dwg

FIELD: electricity.

SUBSTANCE: current collector for water electrolytic cell or fuel element with solid polymer electrolyte that consists of sintered titanium powder of spherical shape is arranged as multilayer. The first layer comprises powder particles, which are identical in size and are selected from the range of 5÷20 mcm, and subsequent layers contain powder particles that vary in size and are selected from the range of 5÷250 mcm. Maximum size of particles in each subsequent layer is more than maximum size of particles in the previous layer, besides content in layers of particles with size of 5÷20 mcm reduces down from 100 wt % in the first layer to 5-10 wt % in the last layer. Method for manufacturing of specified collector includes layer filling of titanium powder into mold and further sintering of layers, besides after each layer has been filled, its intermediate sintering is carried out at 800-950°C, and then all layers are finally sintered at 1000-1200°C.

EFFECT: improved porous structure of collector and increased efficiency of electrochemical systems operation.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to fuel cells with polymer electrolyte. According to the invention, a membrane electrode assembly (MEA) A in a fuel cell with polymer electrolyte is made in a state when there is no boundary between an electrolytic membrane (1) and an electrode catalyst bed (6). Electrolyte particles (2), fine electrolyte particles (3), and electrode catalyst particles (4) of their mixture (5) are deposited on a porous reinforced membrane, forming a layered body (10Ã). Electrolyte particles (2) and fine electrolyte particles (3) are molten by heating the layered body (10Ã) between heating plates (21) and (22), and the porous reinforced membrane is heated by molten electrolyte, forming a reinforced electrolytic membrane. Also the reinforced electrolytic membrane and the electrode catalyst bed (6), which includes electrode catalyst particles (4), are bonded into an agglomerate owing to the molten electrolyte in a state when there is no interlayer boundary, that way forming a membrane electrode assembly.

EFFECT: increased electrical efficiency.

9 cl, 7 dwg

FIELD: electrical engineering.

SUBSTANCE: invention relates to polar plate, in particular to end or bipolar plate for fuel element, and to completing and regular units of fuel-cell battery. In compliance with this invention, polar plate (10, 12) comprises at least one flow field (16) accessible from, at least, one side of polar plate (10, 12). Note here that polar plate (10, 12) incorporates plate (22) with flow field that comprises at least one aforesaid flow field (16) and blank panel (24) with multiple inlet holes (18). Note also that said flow field (16) is accessible through said multiple inlet holes (18). Said blank plate differs from known designs in that said multiple inlet holes (18) are separated by at least one or several reinforcing spacers (20).

EFFECT: reduced deformation of completing and/or regular units of fuel-cell battery.

9 cl, 9 dwg

FIELD: heating systems.

SUBSTANCE: invention refers to fuel element plate with ion-exchange membrane and is intended for being installed on an automobile. According to invention, fuel element plate includes supply channels (2-5) connected to inlet hole (2a) made in the centre of one of plate sides, and discharge channels (6-9) in which reactant fluid medium flow with relatively high concentration and reactant fluid medium flow with relatively low concentration respectively circulate. Supply and/or discharge channels are made on plate symmetrically; at that, supply and discharge channels have similar fractal configurations made complementarily relative to each other for obtaining a network of interconnected channels.

EFFECT: high efficiency and reliability of fuel element.

8 cl, 4 dwg

FIELD: electricity.

SUBSTANCE: invention relates to design of efficient chemical current sources which provide direct conversion of a redox reaction to electrical energy, bypassing the inefficient (accompanied with large losses) burning process. According to the invention, a "jacket" is worn on a widely used fuel cell (FC) of tubular topology, in which a redox reaction is converted to electrical energy, where the jacket is in form of a three-layer split pipe structure, where the inner and the outer layers are current contacts, and the middle layer is a semiconductor structure based on samaric sulphide (SmS). The said "jacket" is a thermoelectric converter (TEC) which can generate emf when heated uniformly. That way, under the effect of excess heat released by the fuel cell, an intrinsic emf arises in the thermoelectric converter, which is summed with the emf of the fuel cell.

EFFECT: increase in efficiency (efficiency of generation of electrical energy) of the combined system by over 20%.

2 cl, 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: metallurgy.

SUBSTANCE: invention relates to a method of obtaining glass-to-metal and metal-ceramic compounds and metal-metal compounds used in solid oxide fuel cells. According to the invention, the compounds are obtained by using a mixture of powders of base glass and metal oxide. Adding some components to the glass used in the composite joints, for instance MgO, that influence on its viscosity and wetting ability ensures a local change in the glass properties near the interface with the metal and at the same time making glass bulk properties including increased coefficient of thermal expansion closer to the properties of the other components of the joint.

EFFECT: high performance, durability and operating safety of the fuel cells.

16 cl, 9 dwg, 2 tbl, 14 ex

Fuel element // 2361328

FIELD: physics.

SUBSTANCE: invention relates to a fuel element with a separator. According to the invention, the fuel element (100) has a junction area, in which a first conducting separator (1), electrolyte strengthening substrate (3) and a second conducting separator (8) are successively joined by hard solders (11) and (12). The electrolyte strengthening substrate (3) is such that, it is bigger than the junction of the first conducting separator (1) and the junction of the second conducting separator (8) at the junction area. The electrolyte strengthening substrate (3) has insulating property at least in the same area where the electrolyte strengthening substrate (3) is in contact with hard solders (11) and (12).

EFFECT: prevention of electrical locking.

6 cl, 7 dwg

FIELD: electricity.

SUBSTANCE: electrolyte contains solution of lithium sals with major anions in polar aprotonic solvents with a specific concentration of background sals. The concentration of background sals is selected so that to be equal or close to concentration of these sals saturated solution in the aprotonic solvents used. The proposed electrolyte may be used electrolyte cells such as secondary (rechargeable) galvanic cells and batteries containing positive active sulphur-based materials.

EFFECT: increasing efficiency and service life.

9 cl, 10 dwg, 4 ex

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: electrical engineering.

SUBSTANCE: invention relates to electrical engineering, particularly to batteries built around lithium chemical current sources (LCCS). In compliance with this invention, LCCS battery comprises tight housing with cover, set of electrically connected LCCSs arranged inside aforesaid housing, and connector assemblies to connect loads and control devices. Note here that set of LCCSs comprises two independent circuits consisting of six LCCSs connected in series. Set of LCCSs can consists of four units, each comprising three LCCSs connected in series. Every two aforesaid units can be connected in parallel. Unit's elements can be arranged so that the planes of LCCS electrode plates stay perpendicular to housing cover plane, while the battery cover seats on heating plate. LCCSs of lithium-fluoro-carbon electrochemical system make aforesaid LCCSs.

EFFECT: improved specific electrical and life characteristics, self-controlled equalisation of currents in parallel branches.

8 cl, 1 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining organic salts, which contain anions of bis(perfluoroalkyl)phosphinate and can be applied in organic synthesis. Difference of claimed method lies in the fact that it includes carrying out reaction of tris(perfluoroalkyl)phosphinoxide with alcohol and organic base, stronger than alcohol.

EFFECT: elaboration of new method of obtaining organic salts with properties of ionic liquids.

11 cl, 14 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: electricity.

SUBSTANCE: invention is attributed to the field of electric engineering, specifically to cathodes of lithium chemical current sources (LCCS). According to the invention LCCS contains sealed body, cover with sealed current taps and filler nozzle, electrode group consisting of anode and cathode plates and separators laid successively, electrolytic solution deposited in sealed body and filling the interelectrode space at that electrode group is placed into polypropylene isolator, cover is provided with recession where filler nozzle and sealed current taps are located. Sealed current taps have outer ring, central metal rod and glass isolator. Sealed current taps can have central metal rod and composite insulator made of fluoroplastic and rubber. To central rods of current taps bridges are welded, cathode bridge is made of titan, anode bridge is made of nickel at that cross-section of titan bridge is twice as large as nickel bridge cross-section.

EFFECT: increase of specific discharge and resource characteristics.

11 cl, 5 dwg

FIELD: electricity.

SUBSTANCE: invention is attributed to the field of electric engineering, specifically to cathodes of lithium chemical current sources (LCCS). According to the invention LCCS cathode contains titan current tap, two electrodes with active mass on the basis of fluorinated hydrocarbon applied onto opposite sides of current tap, and multilayer separator the inner layer of which is made of nonwoven polypropylene at that current tap is made of perforated titan foil 0.03÷0.06 mm in thickness with perforation total area of 0.4÷0.6 of electrode area, the separator additionally contains porous polypropylene film covered from both sides with porous polyethlene film, and glass fabric layer adjoining the inner layer of nonwoven polypropylene separator. Before applying the electrodes current tap surface can be treated by chemical etching or by chemical etching with applying the coatings of colloidal graphite solution or of compound on the basis of glycan or of titan carbide and/or nitride. Active electrode mass is applied on current tap via dry thermal pressing technique at temperature of 150 to 170 °C, pressure of 80÷480 kg/cm2 and time of 25÷60 s. Active electrode mass contains (wt %): fluorocarbon - 80÷90%, fluoroplastic emulsion as binding substance - 2÷5% and carbon black and/or colloidal-graphite preparation as electroconductive additive - the rest.

EFFECT: obtaining of lithium chemical current sources cathodes with improved technical characteristics.

4 cl, 3 dwg, 1 ex

FIELD: electrical engineering.

SUBSTANCE: invention relates to lithium secondary storage battery with electrolyte containing ammonium compounds. In compliance with the invention, the lithium storage battery incorporates a cathode of transfer metal lithium-containing oxide, an anode with graphitised carbon and a nonaqueous solution ammonium admixture producing ammonium ions.

EFFECT: improved performances of storage battery at higher temperature thanks to adding ammonium compounds into electrolyte.

9 cl, 1 tbl, 7 ex

FIELD: chemical power supplies using organic electrolytes.

SUBSTANCE: electrolytes proposed for use in lithium-sulfur batteries has electrolytic salt solutions mixed up with aprotic solvents (primarily sulfones) whose composition corresponds to or is close to eutectic one.

EFFECT: reduced low value of battery operating temperature range.

6 cl, 1 dwg, 1 tbl

FIELD: electrical engineering; manganese dioxide-lithium current supplies.

SUBSTANCE: novelty is that proposed manganese dioxide-lithium current supply has sealed case accommodating at least one positive and at least one negative plates with separator in-between, electrolyte filling plate-to-plate space, and at least one porous heat-sensing component. The latter is made in the form of low-melting inert material layer, minimum 0.13 mm thick, applied directly to entire surface of positive plate facing negative one.

EFFECT: enhanced safety in operation and stability of power characteristics of chemical current supply.

1 cl, 2 dwg

FIELD: electricity.

SUBSTANCE: nano-dimension modified composite material corresponds to structural formula LipFexM1-x(PO4)t(AO4)1-t, where 0<p<2; 0<x<1; 0≤t≤1. In addition, material is doped with cations of the above semi-equivalent elements; at that, for iron positions: - M = Co, Ni, Mg, Ca, Zn, Al, Cu, Ti, Zr; and for phosphate positions: - A=S, Si, V, Mo. Medium linear sizes of crystals of the obtained nano-dimension material is 20-500 nm, thickness of carbon coating is 1-20 nm.

EFFECT: doping of material for iron and phosphorus positions allows increasing concentration of defects in lithium subarray, increasing ionic conductivity and specific power, capacitance and cycling duration of lithium-ion accumulator cells.

4 dwg, 2 tbl

Up!