Method for preparing lithium complex salts for using in chemical current source

FIELD: chemistry of organometallic compounds.

SUBSTANCE: invention relates to a method for preparing lithium complexes salts of the general formula (I): wherein each radical R3-R6 means hydrogen atom (H) or halogen atom (F, Cl or Br). Method involves mixing a) 3-, 4-, 5-, 6-substituted phenol of the formula (III): wherein R3-R6 have above given values with chlorosulfonic acid in acceptable solvent to yield compound of the formula (IV): ; b) intermediate product of the formula (IV) from the stage a) wherein R3-R6 have values given above is subjected for interaction with chlorotrimethylsilane to yield compound of the formula (II) given in the invention description and obtained product is filtered off and subjected for differential distillation; c) intermediate product (II) from the stage b) is subjected for interaction with tetramethanolate borate lithium (1-) in acceptable solvent and the end product (I) is isolated from it. Invention provides the development of a simple method for synthesis of lithium complex salts.

EFFECT: improved preparing method.

3 cl, 4 ex

 

The present invention relates to a method for producing a lithium complex salts and to their use in chemical current sources.

Lithium-ion batteries are the most promising systems for mobile use, e.g. for applications ranging from complex electronic equipment (such as mobile phones, videokamery) to batteries for vehicles driven by electric motors.

These batteries consist of a cathode, anode, separator, and nonaqueous electrolyte. As materials of the cathode, as a rule, use Li(NMEZ)2O4Li(CoMeZ)O2Li(CoNiXMeZ)O2or other intercalating or introducing lithium compounds. The anodes may consist of lithium metal, carbon materials, graphite, graphite carbon materials or other intercalating or introducing lithium compounds or alloys compounds. The used electrolyte is in the form of solutions, including lithium salts such as LiPF6, LiBF4, LiClO4, LiAsF6, LiF3SO3, LiN(CF3SO2)2and LiC(CF3SO2)3and mixtures thereof in an aprotic solvents.

Conventional conductive lithium salts have different disadvantages. Some conductive salts have low resistance to cyclic charge-discharge is m (for example, LiBF4). Other conductive salts are characterized by low thermal stability (for example, LiPF6), a certain conductive salt is unacceptable, in particular due to their toxicity and low environmental security (for example, LiAsF6).

Therefore, in WO 98/07729 described electroconductive salts of the new class, namely litigate complexes. These compounds have shown particularly good results in tests for resistance to cyclic charge-discharge and proved to be particularly stable. In combination with other salts of these complexes show a synergistic stabilizing effect against oxidation.

Description letibit[5-fluoro-2-autoversioning(2)-O,O’]borate(1-) dedicated to the conductive salt, which, if based on its properties should be considered as a very promising conductive salt for use in lithium-ion batteries. However, there is a problem due to the expensive and complex synthesis predecessors.

In the only previously published literature [Speier, The Preparation and Properties of (Hydroxyorgano)silanes and related compounds, J. Am. Chem. Soc. 74 (1952), 1003], related to the synthesis of 2-hydroxybenzenesulfonic acids and their derivatives, announced this as time-consuming in implementation of the three-stage process with the General release of the product within the 40-70%.

Thus, the present invention is to develop a simple method for the synthesis of lithium complex salts.

This problem is solved by using the proposed invention, a method of obtaining a lithium complex salts of General formula

where

R1and R2that are the same or different, are directly connected or indirectly connected via a single or double bond and each, individually or together represents an aromatic ring selected from phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to hexosamines C1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br), or each individually or together represents an aromatic heterocyclic ring selected from pyridyl, pirila and pyrimidyl, which may be unsubstituted or mono - to Tetra-substituted C1-C6the alkyl, C1-C6alkoxyl or a halogen atom (F, Cl, Br),

or each individually or together represents an aromatic ring selected from hydroxybenzomorpholine, hydroxynaphthalenes, hydroxybenzenesulfonic and hydroxyethanesulfonic, which may be unsubstituted or mono - to Tetra-substituted With 1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br),

R3-R6individually or in pairs, being directly or not directly connected to each other via a single or double bond, everyone can have the following meanings:

1) With the1-C6alkyl, C1-C6alkoxy or halogen atom (F, Cl, Br) or

2) an aromatic ring selected from the group including

phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to hexosamines1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br),

pyridyl, Persil and pyrimidyl, which may be unsubstituted or mono - to Tetra-substituted C1-C6the alkyl, C1-C6alkoxyl or a halogen atom (F, Cl, Br),

characterized in that

a) 3-, 4-, 5-, 6-substituted phenol (III) in an acceptable solvent is mixed with chlorosulfonic acid,

b) intermediate product (IV) from step a) is subjected to interaction with chlorotrimethylsilane, and the product is filtered and subjected to fractional distillation,

b) intermediate product (II) from step b) is subjected to interaction with ititernationeliem(1-) in an acceptable solvent and from it produce the final product (I).

When creating nastojasih the invention has been set, what lithium complex salts can be obtained by conducting a 3-step synthesis using as a starting material 3-, 4-, 5-, 6-substituted phenol (III). This source material is a compound of General formula

where R3-R6individually or in pairs, being directly or not directly connected to each other via a single or double bond, everyone can have the following meanings:

1) With the1-C6alkyl, C1-C6alkoxy or halogen atom (F, Cl, Br) or

2) an aromatic ring selected from the group including

phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to hexosamines1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br),

pyridyl, Persil and pyrimidyl, which may be unsubstituted or one - to Tetra-substituted C1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br).

The intermediate product of General formula (II)

where R1and R2each individually or jointly has the following values:

R1, R2denote H, alkyl containing 1-6 C atoms, or trialkylsilyl (contains1-C6Alki is),

R3-R6individually or in pairs, being directly or not directly connected to each other via a single or double bond, everyone can have the following meanings:

1) With the1-C6alkyl, C1-C6alkoxy or halogen atom (F, Cl, Br) or

2) an aromatic ring selected from the group including

phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to hexosamines1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br),

pyridyl, Persil and pyrimidyl, which may be unsubstituted or one - to Tetra-substituted C1-C6alkyl, C1-C6alkoxygroup or a halogen atom (F, Cl, Br),

can be synthesized with a yield of around 80-90%.

The final product of General formula (I) can be used in electrolytes for lithium batteries, either individually or in combination with other lithium salts and/or borate complexes. In this case, it is important to be sure that the sodium content of impurities is very low. Otherwise, taking into account their electrochemical properties (sodium more basic than lithium), the structure of the negative electrodes were introduced would be sodium ions. Eventually it would lead to the exit b is tarei failure. Offer in accordance with the invention, the method can be carried out without the use of sodium.

Therefore, for use in chemical power sources are suitable, in particular, litigate the complexes obtained in accordance with the invention. Litigate complexes can be used in conjunction with other lithium salts, or in another embodiment with borate complexes in electrolytes for lithium rechargeable batteries.

In another embodiment, lithium borate complexes can also be used in electrolytes, including conventional conductive salt. For this purpose, suitable, for example, the electrolyte comprising a conductive salt selected from the group comprising LiPF6, LiBF4, LiClO4, LiAsF6, LiF3SO3, LiN(CF3SO2)2, Li(CF3SO2)3and mixtures thereof. In electrolytes can also enter organic isocyanates (DE 19944603) to reduce the water content. Equally the electrolyte as an additive may include organic salts of alkali metals (DE 19910968). As an example we can mention the borates of alkali metals with the General formula

Li+B-(OR1)m(OR2)p

where

m and p each represents 0, 1, 2, 3 or 4, and m+p=4, and

R1and R2that are the same or different, related or not with who are closely linked to each other directly by means of a single or double bond and each individually or jointly denotes the residue of an aromatic or aliphatic carboxylic, dicarboxylic or sulfonic acid or each individually or together represents an aromatic ring selected from phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to Tetra-substituted a or Hal, or

each individually or together denotes a heterocyclic aromatic ring selected from pyridyl, pirila and bipyridyl, which may be unsubstituted or mono - to tizamidine a or Hal, or

each individually or jointly denotes the residue of an aromatic hydroxy acid selected from aromatic hydroxycarbonic acids and aromatic hydroxysulfonic acids, which may be unsubstituted or mono - to Tetra-substituted a or Hal,

where

Hal denotes F, Cl or Br, a

And denotes alkyl that contains 1-6 C atoms and can be mono - to trihalomethanes.

Equally acceptable alkali metal alcoholate of the General formula

Li+OR-

where

R denotes the residue of an aromatic or aliphatic carboxylic, dicarboxylic or sulfonic acid, or

denotes an aromatic ring selected from phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted or mono - to Tetra-substituted a or Hal, or

denotes a heterocyclic aromatic ring, select the Noah from pyridyl, pirila and bipyridyl, which may be unsubstituted or mono - to tizamidine a or Hal, or

denotes the residue of an aromatic hydroxy acid selected from aromatic hydroxycarbonic acids and aromatic hydroxysulfonic acids, which may be unsubstituted or mono - to Tetra-substituted a or Hal,

where

Hal denotes F, Cl or Br, a

And denotes alkyl that contains 1-6 C atoms and can be mono - to trihalomethanes.

Equally electrolytes may include compounds of the following formula (DE 19941566)

{[[R1(CR2R3)k]1Ax]yKt}+ -N(CF3)2

where

Kt denotes N, P, As, Sb, S, or Se,

And denotes N, P, R(O), O, S, S(O), SO2, As, As(O), Sb or Sb(O)

R1, R2and R3that are the same or different, each represents H, halogen atom, substituted and/or unsubstituted WithnH2n+1alkyl, substituted and/or unsubstituted of alkenyl containing 1-18 carbon atoms and one or more double bonds, substituted and/or unsubstituted quinil containing 1-18 carbon atoms and one or more triple relations, substituted and/or unsubstituted WithmH2m-1cycloalkyl, mono - or polyamidine and/or unsubstituted phenyl, substituted and/or unsubstituted heteroaryl,

thus

And can be included in 1, R2and/or R3in various positions

Kt may contain cyclic or heterocyclic rings,

groups associated with Kt, may be the same or different,

n denotes the number of 1-18

m denotes the number 3-7

k denotes 0 or the number of 1-6

l denotes the number 1 or 2 when x represents 1, and 1 when x represents 0,

x denotes 0, 1

y denotes the number 1-4.

The method of obtaining these compounds are characterized in that the polar organic solvent to carry out the reaction of the alkali metal salt of General formula

where D+choose from the group of alkali metal salt of General formula

where Kt, A, R1, R2, R3, k, l, x and y have the above meanings, and-F denotes the F-, CL-, Br-I-BF

-
4
, ClO
-
4
AsF
-
6
, SbF
-
6
or PF
-
6
.

In addition, it is equally possible to use electrolytes, including compounds of General formula (DE 19953638)

X-(CYZ)m-SO2N(CR1R2R3)2

where

X denotes H, F, Cl, CnF2n+1CnF2n-1or (SO2)kN(CR1R2R3)2,

Y denotes H, F, Cl,

Z represents H, F, Cl,

R1, R2and R3each represents H and/or alkyl, foralkyl, cycloalkyl,

m denotes 0 to 9, if X denotes H, a, m denotes 0,

n denotes 1-9,

k denotes 0, if m denotes 0, and k denotes 1, if m denotes 1-9,

obtained by the reaction of a partially fluorinated or perfluorinated alkylsulfonates with dimethylamine in organic solvents, and complex salts of the General formula (DE 19951804)

MX +[EZ]

y
x/y

where

x and y each represents 1, 2, 3, 4, 5 or 6,

MX +denotes a metal ion,

E denotes a Lewis acid selected from BR1R2R3, AlR1R2R3PR1R2R3R4R5AsR1R2R3R4 5VR1R2R3R4R5where

R1-R5that are the same or different and are directly connected or indirectly connected via a single or double bond, each individually and collectively denotes a halogen atom (F, Cl, Br),

C1-C8alkyl or C1-C8alkoxyalkyl, which may be partially or fully substituted by F, Cl or Br,

aromatic ring which is linked or not linked through the oxygen atom, which is selected from phenyl, naphthyl, anthracene and phenanthrene and which may be unsubstituted or mono - to hexosamines1-C8the alkyl or F, CL or Br, aromatic heterocyclic ring, which is connected or not connected by an oxygen atom, which is selected from pyridyl, pirila and pyrimidyl and which may be unsubstituted or mono - to Tetra-substituted C1-C8the alkyl or F, Cl or Br, and

Z denotes OR6, NR6R7, CR6R7R8, OSO2R6N(SO2R6)(SO2R7), With(SO2R6)(SO2R7) (SO2R8), OCOR6where

R6-R8that are the same or different and are directly connected or indirectly connected via a single or double bond, who each, individually or together represents hydrogen or has the same values and R1-R5,

obtained by the reaction of the corresponding product accession boron or fosforsoderzhashchie Lewis acid and solvent with lithium or tetraalkylammonium-Metricom or a triflate.

May also be present borate salts (DE 19959722) General formula

where

M represents a metal ion or tetraalkylammonium ion,

x and y each represents 1, 2, 3, 4, 5 or 6,

R1-R4which are identical or different, denote C1-C8alkoxy - or1-C8carboxylation and directly linked or indirectly linked via a single or double bond.

These borate salts receive by the interaction of limitedliability or mixture of socialcast with the ester of boric acid in the ratio of 1:1 in an aprotic solvent acceptable hydroxyl or carboxyl compound in the ratio of 2:1 or 4:1.

In the electrolyte composition can be also used supplements that include literaturescientific General formula (I)

where

1≤x≤5

3≤y≤8

0≤z≤2y+1

and the ligands (CyF2y+1-zHz) may be the same or different, with the exception of compounds of General formula (I’)

where and denotes an integer of 2-5, b denotes 0 or 1, p represents 0 or 1, d is 2 and e denotes an integer of 1-4, provided that b and C cannot simultaneously denote 0, and the sum of a+e is equal to 6, and the ligands [CHbFc(CF3)d] the same or different (DE 10008955). The method of producing literaturwerkstatt General formula (I) characterized in that at least one compound of General formula

in each of them

0≤m≤2, 3≤n≤8 and 0≤o≤4,

foryouth by electrolysis in hydrogen fluoride thus obtained a mixture of products of the fluorination is achieved by extraction by phase separation and/or distillation, and the resulting fluorinated alkylphosphoric subjected to interaction with lithium fluoride in an aprotic solvent or solvent mixture that does not contain moisture, and the resulting salt of General formula (I) are purified and isolated in accordance with standard methods.

Such additives can be used in electrolytes for chemical current sources, which include an anode material, which is provided with a coating of metal series is Zevina, selected from the group of Sb, Bi, Cd, In, Pb, Ga and tin, and their alloys (DE 10016024). The method of obtaining this anode material is the fact that

a) urotropine preparing a suspension or Sol of a metal core or a core of alloy

b) this suspension emuleret5-C12hydrocarbons,

C) emulsion precipitated in the form of a metallic core or core alloy and

g) annealing system hydroxides or oxyhydroxides metals are converted into the corresponding oxides.

These additives can also be used in the electrolyte composition for chemical current sources, including the cathodes of conventional compounds, intercalating and introducing lithium, but, alternatively, includes cathode materials, which consist of mixed with lithium oxide particles which are coated with one or more metal oxides (DE 19922522) by suspension of these particles in an organic solvent, mixing the suspension with a solution of a hydrolyzable compound of a metal and a hydrolysis solution with subsequent filtering of coated particles, drying and calcining, if necessary. In another embodiment, they can be mixed with lithium oxide particles which are coated with one or more polymers (DE 19946066)obtained by the method in which the particles are suspended in the solvent, the donkey which coated particles are then filtered, dried and calicivirus, if necessary. Equally additives in accordance with the invention can be used in the system, including cathodes, which consist of mixed with lithium oxide particles that once or repeatedly coated with compounds of alkali metals and metal oxides (DE 10014884). The method of obtaining these materials is characterized by the fact that the particles are suspended in an organic solvent, add a salt of an alkali metal compound, suspended in an organic solvent, add metal oxides, dissolved in an organic solvent, the suspension is mixed with the hydrolyzed solution, after which the coated particles are then filtered, dried and calicivirus.

In more detail below provides a General example of carrying out the invention.

The intermediate product (II):

In the atmosphere of inert gas (argon or nitrogen) 3-, 4-, 5-, 6-substituted phenol (III) is dissolved in an acceptable solvent. Within a time span of 30 min to 2 h at a temperature in the range 10-30°C., preferably at room temperature, the solution is mixed with 5-20%excess chlorosulfonic acid. During the next 20-40 h carry out the reaction, usually within 24 h, the precipitated precipitate the product (IV) filtered vacuum filtration in almost the re inert gas, washed acceptable solvent and dried under vacuum.

This intermediate product (IV) in the atmosphere of inert gas mixed with 1.5 to 4-fold excess (relative to the stoichiometric quantity) of chlorotrimethylsilane and heated to boiling. After completion of intensive Hcl extraction again add the same amount of chlorotrimethylsilane and the solution refluxed for 50-100 hours After cooling in an atmosphere of inert gas drawn into the sediment source material is filtered off. Under a slightly reduced pressure to remove the excess of chlorotrimethylsilane and fractional distillation produce the intermediate product of General formula (II).

The transformation in lithium complex salt:

To obtain a lithium complex salts (I) in the atmosphere of inert gas in the form of the initial portion of the injected limitedlaboratory in a polar aprotic solvent. As a solvent it is possible to use a solvent selected from acetonitrile, acetone, nitromethane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethylcarbonate, diethylmalonate, propylene carbonate, butylaniline and methylethylketone. After the introduction of stoichiometric quantities of an intermediate product (II) the mixture is stirred for a period of time of produces the a to 5 h, preferably 45-90 min, at a temperature in the range of 40-70°C. Under a slightly reduced pressure the resulting silane and the solvent is removed, and the crude product is dried under vacuum to constant weight. This crude product is recrystallized from appropriate solvent or mixture of solvents, and then dried under vacuum to constant weight.

Below the invention is illustrated in the examples, not limiting its scope.

Examples

Example 1

5-fluoro-2-hydroxybenzenesulfonic acid

In nitrogen atmosphere, 200 g (1,78 mole) of 4-terfenol dissolved in 1300 ml of CHCl3(distilled and dried over CaCl2). In this solution at room temperature dropwise over 1 h with stirring, 131 ml (229 g, a 1.96 mole) chlorosulfonic acid. In the beginning see intense emission of Hcl, which is within 30 min after adding fades and after another 3 hours is completely stopped. After 24 h of reaction precipitated precipitated product is filtered off by vacuum filtration under inert gas at room temperature, washed twice, using each time with 200 ml l3and dried in vacuum under a residual pressure of 1333 PA and room temperature for 3 hours

The product is a grayish-white, highly hygroscopic powder.

Output: 302 g (88%).

Melting point: 11-114°C (sealed capillary).

1H-NMR (250 MHz, [D6] DMSO):

δ=6,77 (dd,3JH3-H4=8,9 Hz4JH3-F=4,6 Hz, 1H, H-3),? 7.04 baby mortality (dt,3JH4-H3=8,9 Hz4JH4-H6=3.3 Hz,3JH4-F=a 8.9 Hz, 1H, H-4),

7,16 (dd,3JH6-F=8,4 Hz4JH6-H4=3.3 Hz, 1H, H-6),

12,32 (broad s, 2H, HE, SO3H).

13C-NMR (at 62.9 MHz, [D6] DMSO):

δ=113,46 (+, d2JC-F=24,0 Hz, C-6),

118,47 (+, d3JC-F=7,4 Hz, C-3),

118,53 (+, d2JC-F=23,0 Hz, C-4),

131,79 (CQuartetd,3JC-F=5.8 Hz, C-1),

150,22 (CQuartetd,4JC-F=1,8 Hz, C-2),

155,10 (CQuartetd,1JC-F=236,3 Hz, C-5).

MC (70 eV, E1), m/z (%):

194 (2) [M++2], 193 (3) [M++1], 192 (54) [M+], 174 (44), 126 (23), 110 (65), 98 (15), 82 (100), 63 (16), 57 (20).

C6H5O4FS: the detection. 191,9892 (just msvr (mass spectroscopy high-resolution)).

Example 2

Trimethylsilyl-5-fluoro-2-trimethylsilyldiazomethane

302 g (of 1.57 mol) of 5-fluoro-2-hydroxybenzenesulfonic acid in the atmosphere of inert gas at room temperature with stirring to combine with 794 ml (683 g, 6,28 mole) of chlorotrimethylsilane and the mixture heated to boiling. After attenuation of intense emission of Hcl add 794 ml of chlorotrimethylsilane and turbid solution is refluxed for 96 hours After cooling the precipitate in an inert gas otherthrow who live, at 40-50°C under slightly reduced pressure (about 4000 PA) to remove the excess of chlorotrimethylsilane and fractional distillation under vacuum to obtain the product.

The product is a colorless viscous easily hydrolyzable liquid.

Output: 496 g (93%).

Boiling point: 93-96°C/1,333 PA.

1H-NMR (250 MHz, CDCl3):

δ=0,32 (s, 9H, OTMS),

of 0.36 (s, 9H, OTMS),

6,87 (dd,3JH3-H4=9,0 Hz,4JH3-F=4,3 Hz, 1H, H-3),

7,16 (ddd,3JH4-H3=9,0 Hz,4JH4-H6=3.2 Hz,3JH4-F=7.9 Hz, 1H, H-4),

EUR 7.57 (dd,4JH6-H4=3.2 Hz,3JH6-F=8.0 Hz, 1H, H-6).

13C-NMR (at 62.9 MHz, CDCl3):

δ=0,38 (+, OTMS),

0,43 (+, OTMS),

116,23 (+, d2JC-F=26,4 Hz, C-6),

121,08 (+, d2JC-F=23,0 Hz, C-4),

121,70 (+, d3JC-F=7,4 Hz, C-3),

130,99 (CQuartetd,3JC-F=7,3 Hz, C-1),

149,82 (CQuartetd,4JC-F=2,6 Hz, C-2),

155,77 (CQuartetd,1JC-F=243,2 Hz, C-5).

MS (70 eV, E1), m/z (%): 336 (3) [M+], 321 (33), 264 (43), 249 (60), 233 (96), 169 (39), 147 (59), 75 (100), 73 (76), 45 (18).

C12H21O4FSSi2: the detection. 336,0683 (just msvr).

Elemental analysis data:C(%)N(%)
calculated:42,826,29
found:42,57 6,30

Example 3

Letibit[5-fluoro-2-autoversioning(2-)O,O’] borate(1-)

of 2.81 g (to 19.8 mmole) of limitedlaboratory(1-) in an inert gas suspended in 100 ml of dimethylcarbonate (DMK). By adding 13,35 g (39.7 mmole) of trimethylsilyl)-5-fluoro-2-trimethylsilyldiazomethane formed a clear solution. It is maintained at 45-50°C for one hour, and during this time he becomes slightly turbid. The resulting silane otparivat together with the solvent at 50°C and under a slightly reduced pressure, and the obtained crude product within 24 h at 70°C, dried under vacuum, created by using the oil pump. This crude product is recrystallized four times from toluene/DMK. Turbidity observed during the first two stages of purification, remove by filtration through a glass Frit. Lithium salt is dried to constant weight in a vacuum under a residual pressure of 1-10 PA at a temperature of 70°C.

The resulting product is presented in the form of colorless needle-like crystals.

1H-NMR (250 MHz, [D6] DMSO):

δ=7,08 (dd,3JH3-H4=8,9 Hz4JH3-F=4.4 Hz, 2H, H-3, H-3’),

? 7.04 baby mortality (dt,3JH4-H3=8,9 Hz4JH4-H6=3.2 Hz,3JH4-F=a 8.9 Hz, 2H, H-4, H-4’),

to 7.50 (dd,4JH6-F=3.2 Hz,3JH6-F=a 8.9 Hz, 2H, H-6, H-6’).

13C-NMR (at 62.9 MHz, [D 6] DMSO):

δ=110,6 (+, d2JC-F=25,7 Hz, C-6),

121,3 (+, d3JC-F=22.9 Hz, C-4),

121,4 (+, d3JC-F=7.9 Hz, C-3),

to 125.3 (CQuartet,3JC-F=7,6 Hz, C-1),

148,9 (CQuartet,4JC-F=2.2 Hz, C-2),

155, 2mm (CQuartet,1JC-F=240,0 Hz, C-5).

AAS (atomic absorption spectrophotometry): the lithium content:

calculated: 1,74%; found: 1,75%.

Example 4

Oxidation resistance letibit[5-fluoro-2-autoversion-(2-)O,O’]borate(1-)

In each case, to remove 5 consecutive current-voltage characteristics under cyclic charge-discharge was applied to the measuring cell, consisting of a platinum working electrode, a lithium counter-electrode and lithium comparative electrode. To this end, in the beginning of the potential, since the residual potential was increased at a rate of 10 mV/s to 5 V relative to Li/Li+and then he was returned to the level of residual potential.

Electrolyte: 0,42 mol/kgLmletibit[5-fluoro-2-autoversioning(2-)O,O’]borate(1-) EC/DMK (in the ratio 1:1).

According to measurements relative to Li/Li+the oxidation potential was 4.5 Century

1. A method of obtaining a lithium complex salts of General formula

where

R3-R6each individually denotes H Il is halogen (F, Cl or Br), characterized in that

a) 3-, 4- , 5- , 6-substituted phenol (III)

in which R3-R6have the meanings specified above,

in an acceptable solvent is mixed with chlorosulfonic acid to obtain the compounds of formula (IV)

b) the intermediate product of formula (IV) from step (a)

in which R3-R6have the meanings specified above,

subjected to interaction with chlorotrimethylsilane with obtaining the compounds of formula (II), the resulting product is filtered and subjected to fractional distillation,

b) intermediate product (II) from step b) is subjected to interaction with ititernationeliem(1-) in an acceptable solvent and from it produce the final product (I).

2. The method of obtaining compounds of General formula (II)

where

R3-R6each individually represents H or halogen (F, Cl or Br), characterized in that the carry out stage (a) and (b) of the method according to claim 1.

3. The method according to claim 1, characterized in that in stage C) of the intermediate product (II) is suspended in a polar aprotic solvent.



 

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The invention relates to a group of new bioconjugation complexes of General formula

BAS-L-Bc-L'-(Bc'-L")n-BAS',

where BAS, BAS', BAS"- bioactive ingredients, which may be identical or different; Su and Su' - complexes phenylboric acid; L, L', L" - linkers; n = 0 or 1, three methods for their production, intermediate products used in their synthesis and representing phenylboronic complexing reagents and phenylboronic cross-linking reagents, the method of selection of the desired cell population, as well as set or system containing bioconjugate And, to scroll to the desired population of cells

The invention relates to new biologically active compounds, namely spiroheterocyclic heterocyclic compounds of the formula I

< / BR>
where n is 0 or 1;

m is 0 or 1;

p is 0;

X represents oxygen or sulfur;

Y represents CH, N or NO;

W represents oxygen or H2;

And represents N or C(R2);

G represents N or C(R3);

D represents N or C(R4)

provided that not more than one of A, G and D represents nitrogen, but at least one of Y, a, G, and D represents nitrogen or NO;

R1represents hydrogen or C1-C4-alkyl;

R2, R3and R4are independently hydrogen, halogen, C1-C4-alkyl, C2-C4alkenyl,2-C4-quinil, aryl, heteroaryl, including five - or six-membered aromatic ring with 1 or 2 nitrogen atoms, as well as furyl or morpholyl, HE OS1-C4-alkyl, CO2R1, -CN, -NO2, -NR5R6or R2and R3or R3and R4accordingly, together with part a and G or G and D southwest a hydrogen, WITH1-C4-alkyl, C(O)R7C(O)OTHER8WITH(O)OR9, SO2R10, -NR5R6, (CH3)3Si and phenyl, or may together represent (CH2)jQ(CH2)kwhere Q represents a bond; j is 2 and k is 0 to 2;

R7, R8, R9, R10and R11are independently C1-C4-alkyl, NH2, aryl or its enantiomer,

and their pharmaceutically acceptable salts, and methods for their preparation, intermediate compounds and pharmaceutical compositions, which has an activating effect against nicotine7-acetylcholine receptors and can be used for the treatment and prevention of psychotic disorders and disorders of the type of lower intellectual

The invention relates to new triazinyl compounds of formulas Ia and Ib:

< / BR>
or their salts, where in the formula Ia W represents N or C-CO-R, where R denotes HE OC1-C6alkyl or NR3R4where R3and R4- N or C1-C6alkyl, or formula Ib Az denotes imidazopyridine and in both formulas Ia and Ib R1represents C1-C4alkyl, R2denotes phenyl fragment or 2,5-cyclohexadiene-3,4-ridin-1 silt fragment

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The invention relates to catalysts used for Homo - and copolymerization of ethylene and other olefin hydrocarbons
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