Compounds containing organofluorochlorophosphate anions

FIELD: chemistry.

SUBSTANCE: invention relates to compounds of formula I, production and use thereof to obtain corresponding organophosphinates [Kt]z+ z[(CnHmF2n+1-m)xPCIyF6.x.y]- (I) where [Kt]z+ is an organic cation of formula (1) [NR4]' (1) where R is an optionally phenyl-substituted linear C1-4-alkyl; formula (2) [PR24]+ (2) where R2 is independently C6-14-alkyl; or formula (6) [HetN]z+ (6), where HetNz+ is a heterocyclic cation selected from a group comprising imidazolium, pyrazolium, dihydroimidazolium, pyrrolidinium, triazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, piperazinium, pyrazinium, R1,-R4, denote H or C1-10-alkyl; n=1-4, m=0 to 2n+1, x=1-4, y=1, z=1-2, under the condition that x+y<5.

EFFECT: novel compounds, a method of producing said compounds and use of said compounds to obtain valuable compounds are disclosed.

12 cl, 10 ex

 

The present invention relates to compounds with organophosphate anions, to receive them, and to their use, in particular as ionic liquids.

Ionic liquids or liquid salts are ionic chemical substances, which consist of an organic cation and, typically, an inorganic anion. They do not contain neutral molecules and often have melting points less than 373 K.

Currently, the area of ionic liquids intensively investigated because there are a wide range of applications. Review articles concerning ionic liquids are, for example, R.Sheldon "Catalytic reactions in ionic liquids", Chem. Commun., 2001, 2399-2407; M.J.Earle, K.R.Seddon "Ionic liquids. Green solvent for the future", Pure Appl. Chem., 72 (2000), 1391-1398; P.Wasserscheid, W.Keim "lonische Flüssigkeiten - neue Lösungen für die Übergangsmetallkatalyse", Angew. Chem., 112 (2000), 3926-3945; T. Welton "Room temperature ionic liquids. Solvents for synthesis and catalysis", Chem. Rev., 92 (1999), 2071-2083 or R. Hagiwara, Ya. Ito "Room temperature ionic liquids of alkylimidazolium cations and fluoroanions", J. Fluorine Chem., 105 (2000), 221-227).

Properties of ionic liquids, for example, melting point, thermal and electrochemical stability, viscosity strongly depends on the nature of the anion. In contrast, the polarity and hydrophilicity, respectively lipophilia can be varied by appropriate choice of the pair cation/anion. Therefore there is a critical need for new ion W is dcosta with variable properties which provide additional opportunities for their application.

From EP 0929558, WO 02/085919 and EP 1162204 known salt performanceperformance anions (abbreviated FAP anions). These salts have a high electrochemical and thermal stability and at the same time have a low viscosity. Salt-based fat anions are largely inert and have a greater resistance to hydrolysis than, for example, salts with PF6-anions.

However, it is much more desirable to have available compounds, for example, as reaction medium, after which the reaction could simply be degraded in order to reduce environmental pollution hardly biodegradable compounds.

Therefore, there is a need for new compounds that can be used, such as ionic liquids and at the same time have easy degradability.

Accordingly, the present invention is to provide new compounds which are suitable, for example, as ionic liquids.

This task is solved by means of the compounds according to the invention, the method of their derivation, and their application.

Thus, the first object of the present invention are compounds containing organisors hosphate anions, mostly salt with organophosphate anions. In the sense of the present invention "organic" means each of the organic residue, for example, aliphatic or aromatic organohalide, which themselves in turn can be substituted, for example, other organisatie or residues containing heteroatoms. Relatively organohalides in the framework of the present invention there is no restriction.

In particular, the compounds according to the present invention are each of the formula (I)

In which [Kt]z+means of inorganic or organic cation, with n=1-12, m=0 to 2n+1, x=1-4, y=1-4, z=1-4, and provided that x+y is <5. In the framework of the present invention the means available in the anion Cl-anions. The number of z indicates the degree of charge of the cation and with it the number of available anions in compounds according to the invention. In General, it must be electroneutrality connections.

Preferred compounds according to the invention are each of the formula (I) with m=0 and y=1. These preferred compounds represented by the General formula (Ia):

Particularly preferred x=3 and/or n=2, 3, or 4. In highly preferred within the present invention, compounds selected from the group including the cabbage soup [Kt] z+z[(C2P5)3PClF2]-, [Kt]z+z[(C3F7)3PClF2]-or [Kt]z+z[(C4F9)3PClF2]-.

Regarding the choice of the cation of the compound (I) according to the present invention itself has no restrictions. Thus [Kt]z+to be inorganic or organic cation. Preferably the cations are organic cations and particularly preferred organic cations are selected from the group comprising ammonium cations, phosphonium, Urania, tirone, guanidine or heterocyclic cations. Examples of organic cations are ions of polyamine with the degree of charge z=4.

The ammonium cations can be described, for example, formula (1)

,

and

R each time independently from each other means

N

OR', NR'2, indicating that a maximum of one substituent R in the formula (1) represents OR', NR'2,

with a straight chain or branched alkyl with 1-20 C-atoms,

straight chain or branched alkenyl with 2-20 C-atoms and one or more double bonds,

with a straight chain or branched quinil with 2-20 C-atoms and one or more triple bonds,

saturated, partially or fully unsaturated cycloalkyl with 3-7 C-atoms, the cat is which may be substituted by alkyl groups with 1-6 C-atoms, with one or more R partially or completely can be substituted by Halogens, in particular-F and/or-Cl, or partially by-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH, -SO2X, -SR', -S(O)R', -SO2R', -NO2and, with one or two not adjacent and not α-positioned carbon atoms, R may be replaced by atoms and/or groups of atoms selected from the group of-O-, -S-, -S(O)-, -SO2-, -SO2O-, -C(O)-, -C(O)O-, -N+R'2-,

-P(O)R'o-, -C(O)NR'-, -SO2NR'-, -OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R'with R'=H, no, partially or perfluorinated C1to C18-alkyl, C3to C7-cycloalkyl, unsubstituted or substituted phenyl, and may be X = halogen.

Cations of phosphonium can be described, for example, formula (2)

,

and

R2each time independently from each other means

N, OR' or NR'2

with a straight chain or branched alkyl with 1-20 C-atoms,

straight chain or branched alkenyl with 2-20 C-atoms and one or more double bonds,

with a straight chain or branched quinil with 2-20 C-atoms and one or more triple bonds,

saturated, partially or fully unsaturated cycloalkyl with 3-7 C-atoms which may be substituted by alkyl groups with 1-6 C-atoms, where one or more R partially or completely can be substituted by Halogens, in particular-F and/or-Cl, or partially by-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH, -SO2X, -SR', -S(O)R',

-SO2R', -NO2and one or two not adjacent and not α-positioned carbon atoms, R2may be replaced by atoms and/or groups of atoms selected from the group of-O-, -S-, -S(O)-, -SO2-, -SO2O-, -C(O)-, -C(O)O-, -N+R'2-,

-P(O)R'o-, -C(O)NR'-, -SO2NR'-, -OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R'with R'=N, no, or partially perforated C1to C18-alkyl, C3to C7-cycloalkyl, unsubstituted or substituted phenyl, and may be X = halogen.

However, excluded the cations of the formulae (1) and (2), where all four or three substituent R and R2fully substituted by Halogens, for example, the cation of Tris(trifluoromethyl)methylamine, cation, Tetra(trifluoromethyl)ammonium or a cation, Tetra(nonattorney)ammonium.

Cations Urania can be described, for example, formula (3)

,

and cations tirone formula (4)

,

and

R3to R7each time independently from each other means

N, and N is excluded for R5,

with a straight chain or branched alkyl with 1 to 20 C-atoms,

with a straight chain or branched al is Anil with 2-20 C-atoms and one or more double bonds,

with a straight chain or branched quinil with 2-20 C-atoms and one or more triple bonds,

saturated, partially or fully unsaturated cycloalkyl with 3-7 C-atoms which may be substituted by alkyl groups with 1-6 C-atoms

moreover, one or more of the substituents from R3to R7partially or completely can be substituted by Halogens, in particular-F and/or-Cl, or partially by-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH, -SO2X, -SR', -S(O)R', -SO2R',-NO2and one or two not adjacent and not α-positioned carbon atoms, R3to R7may be replaced by atoms and/or groups of atoms selected from the group of-O-, -S-, -S(O)-, -SO2-, -SO2O-, -C(O)-,

-C(O)O-, -N+R'2-, -P(O)R'o-, -C(O)NR'-, -SO2NR'-, -OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R'with R'=H, no, partially or perfluorinated C1to C18-alkyl, C3to C7-cycloalkyl, unsubstituted or substituted phenyl and X = halogen.

The cations guanidine can be described by the formula (5)

,

and

R8to R13each time independently from each other means

H, -CN, NR'2, -OR'

with a straight chain or branched alkyl with 1 to 20 C-atoms,

straight chain or branched alkenyl with 2-20 C-atoms and one or bore alkemi double bonds,

with a straight chain or branched quinil with 2-20 C-atoms and one or more triple bonds,

saturated, partially or fully unsaturated cycloalkyl with 3-7 C-atoms which may be substituted by alkyl groups with 1-6 C-atoms, with one or more substituents from R8to R13partially or completely can be substituted by Halogens, in particular-F and/or-Cl, or partially by

-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, C(O)X, -SO2OH, -SO2X, -SR', -S(O)R', -SO2R', -NO2and one or two not adjacent and not α-positioned carbon atoms, R8to R13may be replaced by atoms and/or groups of atoms selected from the group of-O-, -S-, -S(O)-, -SO2-, -SO2O-, -C(O)-, -C(O)O-, -N+R'2-, -P(O)R'o-, -C(O)NR'-, -SO2NR'-, -OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R'with R'=N, no, or partially perforated C1to C18-alkyl, C3to C7-cycloalkyl, unsubstituted or substituted phenyl and X = halogen.

Beyond that can be used cations of General formula (6)

and

HetNz+denotes a heterocyclic cation selected from the group

and

the substituents from R1' to R4' each time independently from each other Osnach is o N, F, Cl, Br, J, -CN, -OR', -NR'2, -P(O)R'2, -P(O)(OR')2, -P(O)(NR'2)2, -C(O)R', -C(O)OR', -C(O)X, -C(O)NR'2, -SO2NR'2, -SO2OH, -SO2X, -SR', -S(O)R' -SO2R' and/or NO2, indicating that R1', R3', R4' is H and/or straight chain or branched alkyl with 1-20 C-atoms, straight chain or branched alkenyl with 2-20 C-atoms and one or more double bonds,

with a straight chain or branched alkyl with 1-20 C-atoms,

straight chain or branched alkenyl with 2-20 C-atoms and one or

several double bonds,

with a straight chain or branched quinil with 2-20 C-atoms and one or more triple bonds,

saturated, partially or fully unsaturated cycloalkyl with 3-7 C-atoms which may be substituted by alkyl groups with 1-6 C-atoms, saturated, partially or fully unsaturated heteroaryl, heteroaryl - C1-C6-alkyl or aryl-C1-C6-alkyl,

moreover, the substituents R1', R2', R3' and/or R4' together may also form a cyclic system, and one or more of the substituents from R1' to R4' partially or completely can be substituted by Halogens, in particular-F and/or Cl,

or-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH,

-SO2X, -SR', -S(O)R', -SO2', -NO2and, however, not simultaneously, R1' and R4' should be fully substituted by Halogens, and where one or two not adjacent and are not bound to a heteroatom of the carbon atoms of the substituents from R1' to R4'may be replaced by atoms and/or groups of atoms selected from-O-, -S-, -S(O)-,

-SO2-, -SO2O-, -C(O)-, -C(O)O-, -N+R'2-, -P(O)R'o-, -C(O)NR'-, -SO2NR'-,

-OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R'with R'=H, no, partially or perfluorinated C1to C18-alkyl, C3up With7-cycloalkyl, unsubstituted or substituted phenyl and X = halogen.

Under fully unsaturated substituents in the sense of the present invention also refers to an aromatic substituents.

As the substituents R and R2to R13compounds of formulas (1) to (5) according to the invention together with N preferably taken into account: C1to C20-, in particular C1to C14-alkyl groups, and saturated or unsaturated, i.e. also aromatic, C3to C7-cycloalkyl group which may be substituted by C1to C6is an alkyl group, in particular phenyl.

The substituents R and R2in the compounds of formula (1) or (2) may be the same or different. Preferably the substituents R and R2are the discrepancies between the reference.

The substituents R and R2particularly preferably represent methyl, ethyl, isopropyl, propyl, butyl, sec.-butyl, pentyl, hexyl, octyl, decyl or tetradecyl.

Up to four substituents of the cation guanidine [C(NR8R9)(N(R10R11)(NR12R13)]+can also be cross-connected so that the form monocyclic, bicyclic or polycyclic cations. Without limiting the generality of the examples of such cations guanidine are:

moreover, the substituents from R8to R10and R13can be given before or especially preferred value.

If necessary, carbocycle or the heterocycles listed above cations guanidine can be substituted for another by C1to C6-alkyl, C1to C6alkenyl, -CN, -NO2, F, Cl, Br, I, -OH, -C1-C6-alkoxy, -NR'2, -SR', -S(O)R', -SO2R', -COOH,

-SO2NR'2, -SO2X' or-SO3H, and X and R' have the previously mentioned meaning, substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle can be substituted.

Up to four substituents cation Urania [C(R3R4N)(OR5)(NR6R7)]+or cation tirone [C(R2R4N)(SR5)(NR6R7)]+can also pairs to be with who are closely linked so what form monocyclic, bicyclic or polycyclic cations.

Without limiting the generality of the examples of such cations are shown in further, and Y=O or S means:

moreover, the substituents R3, R5and R6can be given before or especially preferred value.

If necessary, carbocycle or the heterocycles listed previously cations can be substituted for another by C1up With6-alkyl, C1to C6alkenyl, -CN, -NO2, F, Cl, Br, I, -OH, -C1-C6-alkoxy, -NR'2, -SR', -S(O)R', -SO2R', -COOH, SO2NR'2, SO2X or SO3H or substituted or unsubstituted phenyl or unsubstituted or substituted heterocycle, and X and R' have the previously specified value.

The substituents from R3to R13represent each time independently from each other preferably a straight chain or branched alkyl group with 1 to 16 C-atoms. The substituents R3and R4, R6and R7, R8and R9, R10and R11and R12and R13in the compounds of formulas (3) to (5) may be the same or different. Particularly preferred R3to R13each time independently from each other methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, sec.-butyl, phenyl, Huck is silt or cyclohexyl, highly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl or hexyl.

As the substituents from R1' to R4' compounds of the formula (6) according to the invention together with N preferably taken into account: With1to C20in particular, C1up With12-alkyl groups, and saturated or unsaturated, i.e. also aromatic, With3up With7-cycloalkyl group which may be substituted by from C1up With6-alkyl groups, in particular phenyl.

The substituents R1' and R4' are each time independently of one another particularly preferably methyl, ethyl, isopropyl, propyl, butyl, sec.-butyl, tert.-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl or benzyl. Among them highly preferred methyl, ethyl, n-butyl or hexyl. In the compounds of pyrrolidine, piperidine or indoline both Deputy R11and R41preferably different.

Deputy R2' or R3' each time independently from each other is in particular H, methyl, ethyl, isopropyl, propyl, butyl, sec.-butyl, tert.-butyl, cyclohexyl, phenyl or benzyl. Particularly preferred R2is H, methyl, ethyl, isopropyl, propyl, butyl or sec.-butyl. In highly preferred R2' and R3' is N.

<> With1-C12is an alkyl group represents, for example, methyl, ethyl, isopropyl, propyl, butyl, sec.-butyl or tert.-butyl, hereinafter also referred to as pentyl, 1-, 2 - or 3-methylbutyl, 1,1-, 1,2-or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. If necessary, deformity, trifluoromethyl, pentafluoroethyl, heptafluoropropyl or nonattorney.

Straight chain or branched alkenyl with 2 to 20 C-atoms, and may also have multiple double bonds, is, for example, allyl, 2-or 3-butenyl, Isobutanol, Deut.-butenyl, then 4-pentenyl, ISO-pentenyl, hexenyl, heptenyl, octenyl, -C9H17, -C10H19up With20H39; mainly allyl, 2 - or 3-butenyl, Isobutanol, Deut.-butenyl, further preferred 4-pentenyl, ISO-pentenyl or hexenyl.

Straight chain or branched quinil with 2 to 20 C-atoms, and can also be several ternary relations is, for example, ethinyl, 1-or 2-PROPYNYL, 2 - or 3-butenyl, then 4-pentenyl, 3-pentenyl, hexenyl, heptenyl, octenyl, -C9H15, -C10H17up With20H37mainly ethinyl, 1 - or 2-PROPYNYL, 2 - or 3-butenyl, 4-pentenyl, 3-pentenyl or hexenyl.

Aryl-C1-C6-alkyl means, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, fenilpentil or phenylhexa is, both the phenyl ring and Allenova chain, as described previously, can be replaced partially or completely by Halogens, in particular-F and/or-Cl, or partially by-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH, -SO2X, -SR', -S(O)R', -SO2R', -NO2.

So unsubstituted saturated or partially or fully unsaturated cycloalkyl group having 3-7 C-atoms are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopent-1,3-dienyl, cyclohexenyl, cyclohexa-1,3-dienyl, cyclohexa-1,4-dienyl, phenyl, cycloheptenyl, cyclohepta-1,3-dienyl, cyclohepta-1,4-dienyl or cyclohepta-1,5-dienyl, which can be substituted C1up With6-alkyl groups, and again cycloalkyl group or substituted C1up With6-alkyl groups cycloalkyl group can also be substituted by halogen atoms such as F, Cl, Br or I, in particular F or Cl, or by-OH, -OR', -NR'2, -CN, -C(O)OH, -C(O)NR'2, -SO2NR'2, -C(O)X, -SO2OH, -SO2X, -SR', -S(O)R' -SO2R', -NO2.

In the substituents R, R2to R13or R1' to R4' one or two not adjacent and not α-located to the heteroatom bound to carbon atoms may be replaced by atoms and/or groups of atoms, wybran the mi from the group-O-, -S-, -S(O)-,

-SO2-, -SO2O-, -C(O)-, -C(O)O-, -N+R'2-, -P(O)R'o-, -C(O)NR'-, -SO2NR'-,

-OP(O)R'o-, -P(O)(NR'2)NR'-, -PR'2=N - or-P(O)R', with R' = not, partially or perfluorinated C1up With18-alkyl, C3up With7-cycloalkyl, unsubstituted or substituted phenyl.

Without limiting the generality of examples for this kind of modified substituents R, R2to R13and R1' to R4' are: -co3,

-Och(CH3)2, -CH2OCH3, -CH2-CH2-O-CH3, -C2H4OCH(CH3)2, -C2H4SC2H5,

-C2H4SCH(CH3)2, -S(O)CH3, -SO2CH3, -SO2C6H5, -SO2C3H7, -SO2CH(CH3)2,

-SO2CH2CF3, -CH2SO2CH3, -O-C4H8-O-C4H9, -CF3, -C2F5, -C3F7, -C4F9- (CF3)3,

-CF2SO2CF3, -C2F4N(C2F5)C2F5, -CHF2, -CH2CF3, -C2F2H3, -C3FH6, -CH2C3F7- (CFH2)3, -CH2(O)HE, -CH2With6H5-C(O)6H5or P(O)(C2H5)2.

R' is a C3up With7-cycloalkyl, for example, Cyclops is sawdust, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

R' represents substituted phenyl, via C1up With6-alkyl, C1up With6alkenyl, -CN, -NO2, F, CI, Br, I, -OH, -C1-C6-alkoxy, NR2, -COOH, -SO2X', -SR", -S(O)R", -SO2R", SO2NR2or SO3H substituted phenyl, and X' is F, Cl or Br and R" denotes not, partially or perfluorinated C1up With6-alkyl or C3up With7-cycloalkyl as defined for R', for example, o-, m - or p-were, o-, m - or p-ethylphenyl, o-, m - or p-propylphenyl, o-, m - or p-isopropylphenyl, o-, m - or p-tert-butylphenyl, o-, m - or p-nitrophenyl, o-, m - or p-hydroxyphenyl, o-, m - or p-methoxyphenyl, o-, m - or p-ethoxyphenyl, o-, m-, p-(trifluoromethyl)phenyl, o-, m-, p-(triptoreline)phenyl, o-, m-, p-(trifloromethyl)phenyl, o-, m - or p-forfinal, o-, m - or p-chlorophenyl, o-, m - or p-bromophenyl, o-, m - or p-iopener, further preferably 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3.5-dimetilfenil, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dihydroxyphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-differenl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dibromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-acid, 5-fluoro-2-were, 3,4,5-trimethoxyphenyl or 2,4,5-trimetilfenil.

In R1' to R4' as heteroaryl refers to saturated or unsaturated monocyclic or bicyclic heterocyclic estato is from 5 to 13 ring members, and can be 1, 2 or 3 N and/or 1 or 2 S or O atoms and the heterocyclic residue once or repeatedly can be replaced by C1up With6-alkyl, C1up With6alkenyl, -CN, -NO2, F, Cl, Br, I, -OH, -NR2, - C1-C6-alkoxy, -COOH, -SO2X' -SO2NR2, -SR", -S(O)R", -SO2R" or SO3H, where X' and R" have the previously specified value.

Heterocyclic residue is a predominantly substituted or unsubstituted 2 - or 3-furyl, 2 - or 3-thienyl, 1-, 2 - or 3-pyrrolyl, 1-, 2-, 4 - or 5-imidazolyl, 3-, 4 - or 5-pyrazolyl, 2-, 4 - or 5-oxazolyl, 3-, 4 - or 5-isoxazolyl, 2-, 4 - or 5-thiazolyl, 3-, 4 - or 5-isothiazole, 2-, 3-or 4-pyridyl, 2-, 4-, 5 - or 6-pyrimidinyl, further preferably 1,2,3-triazole-1-, -4 - or-5-yl, 1,2,4-triazole-

1-, -4 - or-5-yl, 1 - or 5-tetrazolyl, 1,2,3-oxadiazol-4 - or-5-yl 1,2,4-oxadiazol-3 - or-5-yl, 1,3,4-thiadiazole-2 - or-5-yl, 1,2,4-thiadiazole-3 - or-5-yl, 1,2,3-thiadiazole-4 - or-5-yl, 2-, 3-, 4-, 5 - or 6-2H-dipiradol, 2-, 3- or 4-4H-dipiradol, 3 - or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6 - or 7-benzofuran, 2-, 3-, 4-, 5-, 6 - or 7-benzothiazyl, 1-, 2-, 3-, 4-, 5-, 6 - or 7-1H-indolyl, 1-, 2-, 4 - or 5-benzimidazolyl, 1-,

3-, 4-, 5-, 6 - or 7-benzimidazolyl, 2-, 4-, 5-, 6 - or 7-benzoxazolyl, 3-, 4-, 5-, 6 - or 7-benzisoxazole, 2-, 4-, 5-, 6 - or 7-benzothiazolyl, 2-, 4-, 5-, 6 - or 7-benzisothiazolin,

4-, 5-, 6 - or 7-benzo-2,1,3-oxadiazole, 1-, 2-, 3-, 4-, 5-, 6-, 7-yl) - Rev. 8-chinoline, 1-, 3-, 4-, 5-, 6-, 7 - or 8-ethenolysis, 1-, 2-, 3-, 4-or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8 - or 9-acridine, 3-, 4-, 5-, 6-, 7 - or 8-indolinyl, 2-, 4-, 5-, 6-, 7 - or 8-hintline or 1-, 2 - or 3-pyrrolidinyl.

Under heteroaryl-C1-C6the alkyl can now be understood by analogy with aryl-C1-C6-alkyl, for example, pyridinyl-methyl, pyridinyl-ethyl, pyridinyl-propyl, pyridinyl-butyl, pyridinyl-pentyl, pyridinyl-hexyl, and further described previously heterocycles thus may be associated with alkalinous chain.

HetNz+preferably represents

moreover, the substituents from R1' to R4' each time independently from each other have the previously described meaning.

In another form of implementation of the present invention the cation [Kt]z+can be [(Ro)3O]+-cation or [(Ro)3S]+-cation, and Romeans a straight chain or branched alkyl group with 1-8 C-atoms, or unsubstituted phenyl or phenyl substituted by R°, ORoN(Ro)2CN or halogen.

Rocation [(Ro)3O]+or cation [(Ro)3S]+is a predominantly straight chain alkyl with 1-8 C-atoms, preferably 1-4 C-atoms, in particular methyl or ethyl, most preferred ethyl.

The cation [Kt]z+moreover it can also be inorganic, especially when it comes to the metal cation. The metal cation may include metals of groups 1 to 12 of the Periodic system of elements, in particular alkali metals. Preferably the metal is selected from the group comprising Li, K, Rb, Cs.

Preferably the cations of the compounds according to the invention are ammonium cations, phosphonium, guanine or heterocyclic cations, particularly preferably a heterocyclic cations (HetNz+). HetNz+especially preferred is imidazole, pyrrolidine or pyridine, as defined previously, and the substituents from R1' to R4' each time independently from each other have the previously described meaning. HetNz+highly preferred is imidazole, and the substituents from R1' to R4' each time independently from each other have the previously described meaning. Highly preferred compounds according to formula (I) are the salts imidazole, pyrrolidine, pyridinium, ammonium, phosphonium, guanidine with [(C2F5)3PClF2]"-, [(C3F7)3PClF2]-- or [(C4F9)3PClF2]--anions.

Needless to say, to a person skilled in the art that sedimentogene invention deputies, such as, for example, C, H, N, O, Cl, F can be replaced by the corresponding isotopes.

Equally the object of the present invention are methods of producing compounds with organophosphate anions, including interaction of the chloride salt organophosphonate. Preferably according to the invention methods are each to obtain the compounds of formula (I)as described above, including interaction [Kt]z+z[Cl]-with a compound of General formula (II)

in which [Kt]z+means of inorganic or organic cation with z=1-4, and the compounds of formula II, n=1-12, m=0 to 2n+1, x=1-4 and y=1-4. Preferably is y=1 and m=0, i.e. preferably [Kt]+Cl-interacts with the compound of General formula (IIa)

in which [Kt]+means of inorganic or organic cation of the formula IIa means n=1-12 and x=1-4.

Getting perftoruglerodov (formula (II), respectively (IIa)) as starting compounds for the method according to the invention is known to the specialist in the art from the prior art, for example, from German patent application DE 19846636 A1, which thereby is introduced as a reference and thus is effective as part of disclosure.

The method according to the invention can be carried out when the temperature is from -40 to 180°C, mainly the interaction is carried out at from 0 to 50°C and highly preferably at room temperature.

The interaction occurs in particular in the solvent, but can also be carried out in the absence of solvent.

Suitable solvents are each selected from the group NITRILES, dialkylammonium, Klimov, simple dialkylated ethers, simple cyclic ethers, dimethylformamide, dimethylsulfoxide, dichloromethane, water or mixtures thereof. Preferred examples of suitable solvents are acetonitrile and slimy.

The duration of reaction is usually from 5 minutes to 24 hours, mainly from 1 hour to 10 hours.

After the interaction of the compounds according to the invention can be utilized as known to a person skilled in the art the manner and purified, for example by removal of volatiles in vacuo and drying, and if necessary, may be followed by additional purification stages.

Many of the above according to the invention of compounds suitable for use as ionic liquids, respectively, are predominantly ionic liquids and thus can be used in many application systems.

In addition, an object of the present invention is applied to any smooth surface is of the compounds according to the invention as solvents or additives to the solvent, as phase transfer catalysts, as extracting agents, as heat transfer fluids, as surfactants, as a plasticizer, as a flame retardant funds as additive or as a salt, which increases the conductivity of the electrolyte and catalysts in chemical processes.

In the case of the use of these compounds as a solvent, these are suitable in every well-known specialist in the art kind of reaction, for example, catalyzed by transition metals or of enzyme-catalyzed reactions, such as reactions of hydroformylation, reactions of the Friedel-Kraft, oligomerization reactions, formation of esters or isomerization reactions, and the following list is not final.

When used as extracting agents, the compounds may be used for separating the reaction products, but also for the separation of impurities, depending on what is the solubility of the corresponding component used according to the invention the connection. Moreover, the compounds of formula (I) can also serve as a separating means for separating multiple components, for example, the separation by distillation of several components of the mixture.

Other possible applications are upotrebleny is as plasticizers in polymeric materials as the flame retardant agent for a range of materials or applications, as well as salt, which increases the conductivity of the electrolyte in various electrochemical cells and applications, for example, in galvanic cells, capacitors, or fuel cells.

Electrolytes, electrochemical cells, capacitors, or fuel cells containing at least according to the invention one compound of General formula (I), are equally the object of the present invention. In these applications, the compounds according to the invention can be used in combination with all well-known expert in the field of engineering materials and additives, without requiring any special ingenuity on the part of the technician.

Moreover, the compounds according to the invention is suitable for obtaining organophosphinates. In the case of water as a solvent formed first organophosphate can further react with water during the formation of the corresponding organophosphinates. Alternative organophosphonate can also be obtained by the fact that according to the invention obtained organophosphate dissolved in water. Accordingly, organophosphate according to the invention is suitable when applying it to obtain organophosphinates. These organophosphonate again presented with the battle complete connection you can use, such as ionic liquids. Relevant organophosphonate known, for example, from WO 2003/087110, the disclosure of which is hereby entered by reference.

The methods according to the invention to obtain organophosphinates include the interaction of the compounds according to the present invention with water or water-containing solvents or mixtures of solvents. This interaction can occur at temperatures from -40 to 200°C at atmospheric pressure for pressures up to 100 bar. Preferably, the interaction occurs with water at room temperature and atmospheric pressure.

And without other forms of exercise come from the fact that the specialist in the art the above description may be used in the widest sense. Therefore, the preferred forms of implementation and examples are only descriptive, in no way perceived as in any way limiting the disclosure.

Examples

Example 1: Tris(pentafluoroethyl)diperchlorate tetrabutylammonium

A mixture of 7.04 g (25.3 mmol) of tetrabutylammonium chloride and 12.0 g (28.2 mmol) of Tris(pentafluoroethyl)dipterofauna dissolved in 20 ml of acetonitrile and at room temperature, stirred for one hour. Volatile components (excess Tris(pentafluoroethyl)ditto is phosphorane and acetonitrile) is removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature). Obtain 17.0 g of a viscous oily material. The yield of Tris(pentafluoroethyl)diperchlorate tetrabutylammonium is 95.5%, in terms of used tetrabutylammonium chloride. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 0.961 (CH3), 1.35 t,q (CH2), 1.59 m (CH2), 3.06 m (CH2); J3H,H=7.4 Hz.

19F NMR spectrum, ppm million: -at 25.52 d,m (PF), -69.83 d,m (PF), -77.49 t (CF3), -80.04 m (2CF3), -105.12 d,d (CF2FA), -105.87 d,d (CF2FA), -108.89 d,m (CF2), -114.72 d,m (CF2FA), -115.45 d,m (CF2FB), J1P,F=933 Hz, J1P,F=863 Hz, J2P,F=98 Hz, J2P,F=82 Hz, J2P,F=116 Hz,

J2A,B=281 Hz, J4F,F=21 Hz.

31P NMR spectrum, ppm million: -147.4 d,d,m.

Example 2: Tris(pentafluoroethyl)diperchlorate of benzyltriethylammonium

A mixture of 11.45 g (50.3 mmol) of the chloride of benzyltriethylammonium and 2.3.6 g (55.4 mmol) of Tris(pentafluoroethyl)dipterofauna dissolved in 30 ml of acetonitrile and at room temperature, stirred for one hour. Volatile components (excess Tris(pentafluoroethyl)dipterofauna and acetonitrile) is removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature) to Obtain 32.3 g of a viscous, oily material. The yield of Tris(pentafluoroethyl)diperchlorate of benzyltriethylammonium is 98.2%, in terms of used chloride of benzyltriethylammonium. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 1.34 t,t (SN3), 3.14 q (3CH2), 4.30 s (CH2), 7.44-7.58 m (C6H5); J1H,H=7.3 Hz.

19F NMR spectrum, ppm million: -at 25.52 d,m (PF), -69.81 d,m (PF), -77.47 t (CF3), -80.03 m (2CF3), -105.11 d,d (CF2FA), -105.85 d,d (CF2FB), -At 108.87 d,m (CF2), -114.72 d,m (CF2FA), -115.45 d,m (CF2FB), J1P,F=928 Hz, J1P,F=861 Hz, J2P,F=99 Hz, J2P,F=82 Hz, J2P,F=116 Hz, J2A,B=280 Hz, J2F,F=21 Hz.

31P NMR spectrum, ppm million: -147.4 d,d,m.

Example 3: Tris(pentafluoroethyl)diperchlorate 1-ethyl-3-methylimidazole

A mixture of 4.1 g (28.0 mmol) of the chloride of 1-ethyl-3-methylimidazole and 13.1 g (30.8 mmol) of Tris(pentafluoroethyl)dipterofauna stirred at room temperature for three hours. Volatile components (excess Tris(pentafluoroethyl)dipterofauna) removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature). Obtain 15.9 g of a viscous oily material. The yield of Tris(pins shall aftorety)diperchlorate 1-ethyl-3-methylimidazole is 99.2%, in terms of used chloride, 1-ethyl-3-methylimidazole. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 1.45 t (CH3); 3.83 s (CH3); 4.17 q (CH2); 7.37 m (CH); 7.43 m (CH); 8.57 br. s. (CH);3J1H,H=7.3 Hz.

19F NMR spectrum, ppm million: -at 25.52 d,m (PF), -69.83 d,m (PF), -77.48 t (CF3), -80.04 m (2CF3), -105.12 d,d (CF3FA), -105.87 d,d (CF2FB), -At 108.87 d,m (CF2), -114.72 d,m (CF2FA), -115.47 d,m (CF2FB), J1P,F=933 Hz, J1P,F=863 Hz, J2P,F=98 Hz, J2P,F=84 Hz, J2P,F=119 Hz, J2A,B=281 Hz, J4F,F=21 Hz.

31P NMR spectrum, ppm million: -147.4 d,d,m.

Example 4: Tris(pentafluoroethyl)diperchlorate 1-butyl-1-methylpyrrolidine

A mixture of 4.03 g (22.7 mmol) of the chloride 1-butyl-1-methylpyrrolidine and 10.8 g (25.4 mmol) of Tris(pentafluoroethyl)dipterofauna stirred at room temperature for three hours. Volatile components (excess Tris(pentafluoroethyl)dipterofauna) removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature). 13.6 g of a viscous, oily material was obtained. The yield of Tris(pentafluoroethyl)diperchlorate 1-butyl-1-methylpyrrolidine is 99.2%, in terms of ispolzuemyi chloride 1-butyl-1-methylpyrrolidine. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 0.96 t (CH3), 1.36 t,q (CH2), 1.69 m (CH2), 2.14 m (2CH2), 2.93 s (CH3), 3.21 m (CH2), 3.39 m (2CH2); J4H,H=7.4 Hz.

19F NMR spectrum, ppm million: -at 25.52 d,m (PF), -69.81 d,m (PF), -77.48 t (CF3), -80.03 m (2CF3), -105.13 (d,d (CF2FA), -105.87 d,d (CF2FB), -108.89 d,m (CF2), -114.72 d,m (CF2FA), -115.45 d,m (CF2FB), J1P,F=931 Hz, J1P,F=861 Hz, J2P,F=98 Hz, J2P,F=82 Hz, J2P,F=116 Hz, J2A,B=281 Hz, J4F,F=21 Hz.

31P NMR spectrum, ppm million: -147.4 d,d,m.

Example 5: Tris(pentafluoroethyl)diperchlorate trioxymethylene

A mixture of 6.57 g (12.7 mmol) of the chloride trioxymethylene and 5.92 g (13.9 mmol) of Tris(pentafluoroethyl)dipterofauna stirred at room temperature for three hours. Volatile components (excess Tris(pentafluoroethyl)dipterofauna) removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature). 11.96 g of a viscous, oily material was obtained. The yield of Tris(pentafluoroethyl)diperchlorate trioxymethylene 99.6%, in terms of used chlorotrimethylsilane. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 0.90 m (SN3), 1.28 m (8CH2), 1.31 m (8CH2), 1.37-1.55 m (8CH2), 1.97-2.07 m (4CH2).

19F NMR spectrum, ppm million: -25.53 d,m (PF), -69.85 d,m (PF), -77.501 (CF3), -80.06 m (2CF3), -105.15 d,d (CF2FA), -105.89 d,d (CF2FB), -108.91 d,m (CF2), -114.76 d,m (CF2FA), -115.49 d,m (CF2FB), J1P,F=931 Hz, J1P,F=861 Hz, J2P,F=98 Hz, J2P,F=84 Hz, J2P,F=123 Hz, J2A,B=280 Hz, J4F,F=21 Hz.

31P NMR spectrum, ppm million: 33.4 (1P), -147.4 d,d,m (1P).

Example 6: di[Tris(pentafluoroethyl)-diperchlorate tetrakis(dimethylamino)ethylidene

A mixture of 1.6 g (5.9 mmol) dichloride, tetrakis(dimethylamino)ethylidene and 5.6 g (13.1 mmol) of Tris(pentafluoroethyl)dipterofauna dissolved in 20 ml of acetonitrile and at room temperature, stirred for one hour. Volatile components (excess Tris(pentafluoroethyl)dipterofauna and acetonitrile) is removed in vacuum and the residue is dried in vacuum for two hours at 7 PA and at 40-50°C (oil bath temperature). Obtain 6.6 g of a viscous oily material. Output di[Tris(pentafluoroethyl)diperchlorate]tetrakis(dimethylamino)ethylidene is 99.7%conversion is used dichloride, tetrakis(dimethylamino)ethylidene. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 3.14 s (2CH3), 3.43 s (2CH3).

19F NMR spectrum, ppm million: -at 25.52 d,m (PF), -69.83 d,m (PF), -77.46 t (CF3), -80.00 m (2CF3), -105.07 d,d (CF2FA), -105.82 d,d (CF2FB), -108.85 d,m (CF2), -114.68 d,m (CF2FA), -115.45 d,m (CF2FB), J1P,F=933 Hz, J1P,F=861 Hz, J2P,F=96 Hz, J2P,F=82 Hz, J2P,F=120 Hz, J2A,B=282 Hz, J4F,F=21 Hz.

31P NMR spectrum, ppm million: -147.3 d,d,m.

Example 7: Tris(heptafluoropropyl)diperchlorate 1-butyl-1-methylpyrrolidine

A mixture of 1.10 g (6.19 mmol) of the chloride 1-butyl-1-methylpyrrolidine and 3.57 g (6.19 mmol) of Tris(heptafluoropropyl)dipterofauna dissolved in 5 ml of acetonitrile and stirred at room temperature for three hours. The acetonitrile removed in vacuo, and the residue is dried in vacuum for one hour at 7 PA and room temperature. Obtain 4.31 g of a viscous oily material. The yield of Tris(pentafluoroethyl)diperchlorate 1-butyl-1-methylpyrrolidine is 92.4%. The compound analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 0.951 (CH3), 1.36 t,q (CH2), 1.71 m (CH2), 2.14 m (2CH2), 2.93 s (SN 3), 3.22 m (CH2), 3.40 m (2CH2); J4H,H=7.4 Hz.

19F NMR spectrum, ppm million: -at 24.42 d,m (PF), -67.12 d,m (PF), -79.57 m (3CF3), -102.35 d (CF2FA), -103.12 d (CF2FB), -105.71 d,m (CF2), -111.98 d,m (CF2FA), -112.76 d,m (CF2FB), -120.98 t (CF2), -124.11 m (CF2), -124.29 m (CF2), J1P,F=937 Hz, J1P,F=882 Hz, J2P,F=101 Hz, J2P,F=82 Hz, J2P,F=119 Hz, J2A,B=287 Hz.

31P NMR spectrum, ppm million: -139.3 (d,d,m.

Example 8: Tris(pentafluoroethyl)diperchlorate of Tetramethylammonium

A mixture of 0.68 g (6.20 mmol) of the chloride of Tetramethylammonium and 2.65 g (6.22 mmol) of Tris(pentafluoroethyl)dipterofauna dissolved in 5 ml of acetonitrile and stirred at room temperature for ten hours. Volatile components (excess Tris(pentafluoroethyl)-dipterofauna and acetonitrile) is removed in vacuum and the residue is dried in vacuum for 0.5 hour at 7 PA and room temperature. Obtain 3.26 g of solid material. The yield of Tris(pentafluoroethyl)diperchlorate of Tetramethylammonium is 98.2%, in terms of used chloride of Tetramethylammonium. Connection (three different isomer) analyzed by NMR spectrometry.

These NMR:

1H NMR spectrum, ppm million: 3.07 s (SN3).

19F NMR with whom CTR (facial isomer), part./million: -68.9 br.d (PF2), -Area of 78.25 m (2CF3), -78.85 m (CF3), -106.2 br.m (CF2), -112.4 m (2CF2), J1P,F=960 Hz.

19F NMR spectrum (meridional isomer 1), part./million: -22.44 d,m (PF2), -78.2 m (2CF3), -81.3 m (CF3), -106.2 br.m (CF2), -108.0 d,m (2CF2), J2P,F=873 Hz, J2P,F=85 Hz.

19F NMR spectrum (meridional isomer 2), part./million: -25.50 d,m (PF), -69.83 d,m (PF), -77.48 t (CF3), -80.03 m (2CF3), -105.12 d,d (CF2FA), -105.87 d,d (CF2FB), -At 108.87 d,m (CF2), -114.69 last d,m (CF2FA), -115.42 d,m (CF2FB), J1P,F=928 Hz, J1P,F=861 Hz, J2P,F=100 Hz, J2P,F=82 Hz, J2P,F=116 Hz, J2A,B=282 Hz, J4F,F=22 Hz.

31P NMR spectrum, ppm million: -137.0 t,m (facial isomer), -147.3 d,d,m (meridional isomer 2), -149.9 t,m (meridional isomer 1).

Example 9: Tris(pentafluoroethyl)diperchlorate 1-butyl-1-methylpyrrolidine

0.60 g (3.38 mmol) chloride 1-butyl-1-methylpyrrolidine dissolved in 0.61 g of water at room temperature. To this solution is added dropwise 1.44 g (3.38 mmol) of Tris(pentafluoroethyl)dipterofauna at room temperature for minutes. The reaction mixture was stirred 20 min at room temperature. Produces bright, the bottom phase liquid product, Tris(integtrated)diperchlorate 1-butyl-1-methylpyrrolidine, which is (1.77 g) and examined by a spectroscope.

These NMR:

19H NMR spectrum (facial isomer), solvent - water, e-standard (CCl3F), part./million: -80.88 br.s, (CF3), -82.15 br.s, (2CF3), -87.09 br.d (PF2), -114.71 br.d (3CF2), J2P,F=87 Hz, J1P,F=845 Hz.

31P NMR spectrum (facial isomer), solvent - water, e-standard (H3PO4), part./million: -147.7 t.hep.

Example 10: bis(pentafluoroethyl)phosphinate 1-ethyl-3-methylimidazole

0.21 g (0.36 mmol) of bis(pentafluoroethyl)perchlorate 1-ethyl-3-methylimidazole mixed with 2.0 g of water. After approx. 20 min of intense mixing, the mixture becomes homogeneous. Then all volatile components are removed under high vacuum. As a balance remains 0.15 g of oil, which is investigated by a spectroscope.19F NMR spectrum and31F NMR spectrum shows the formation of bis(pentafluoroethyl)phosphinate 1-ethyl-3-methylimidazole.

These NMR:

19F NMR spectrum, solvent - water, e-standard (CCl3F), part./million: -81.26 s, (2CF3), -126.42 d (2CF2), J2P,F=77 Hz.

1. The compound containing organophosphate anions, representing a compound of formula (I)

in which [Kt]z+means organic cation, using the p group, including the cations ammonium, phosphonium or heterocyclic cation, and ammonium cation corresponds to the formula (1)

and R each time independently from each other mean C1-4-alkyl straight chain, which can be substituted by phenyl;
moreover, the cation of the phosphonium corresponds to the formula (2)

and R2each time independently from each other mean With6-14-alkyl;
and heterocyclic cation corresponds to the formula (6)

and HetNz+denotes a heterocyclic cation selected from the group including
or
moreover, the substituents from R1'to R4'each time independently from each other mean is N or C 1-10-alkyl straight or branched chain;
n=1-4, m=0 to 2n+1, x=1-4, y=1, z=1-2 and provided that x+y is <5.

2. The compound according to claim 1, characterized in that m=0 and y=1.

3. The compound according to claim 1 or 2, characterized in that x=3.

4. The compound according to claim 1 or 2, characterized in that n=2, 3, or 4.

5. The compound according to claim 1 or 2, characterized in that the compound of formula (I) selected from the group comprising [Kt]z+z[(C2F5)3PClF2]-, [Kt]z+z[(C3F7)3PClF2]-or [Kt]z+z[(C4F9)3PClF2]-.

6. The compound according to claim 1, characterized in that [Kt]z+represents an ammonium cation, which corresponds to the formula (1)

and R each time independently from each other mean C1-4-alkyl straight chain.

7. The compound according to claim 1, characterized in that [Kt]z+represents a cation of phosphonium, which corresponds to the formula (2)

and R2each time independently from each other mean With7-14-alkyl.

8. The compound according to claim 1, characterized in that [Kt]z+corresponds to the formula (6)

and HetNz+denotes a heterocyclic cation selected from the group including



or

moreover, the substituents from R1'to R4'each time independently from each other denote H or C1-9-alkyl straight or branched chain.

9. The method of obtaining compounds with organophosphate anions according to claims 1-8, including the interaction of the chloride salt organophosphorous carried out at room temperature.

10. The method according to claim 9, characterized in that the interaction occurs in a solvent.

11. The method according to claim 9, wherein the solvent is selected from the group NITRILES, dialkylammonium, Klimov, simple dialkylated ethers, simple cyclic ethers, dimethylformamide, dimethylsulfoxide, dichloromethane, water or mixtures of them.

12. The use of compounds according to one of claims 1 to 8 to obtain the appropriate organophosphinates.



 

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The invention relates to a new method of obtaining perphosphate lithium General formula (I), where a = 1, 2, 3, 4, or 5, b = 0 or 1, C = 0, 1, 2 or 3, d = 0, 1, 2 or 3; e = 1, 2, 3, or 4, provided that the sum of a+e = 6, the sum of b+c+d = 3, and b and C are not simultaneously denote 0, provided the ligands (CHbFc(CF3)d) can be different, and monochlor - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales subjected to electrochemical fluorination in an inert solvent, the resulting mixture of products if necessary, divide by distillation at various fluorinated products and the fluorinated alkylphosphine, put in an aprotic, polar solvent at from -35 to 60oWith interaction with lithium fluoride

FIELD: chemistry.

SUBSTANCE: method involves treating a water-based medium containing sulphate-reducing bacteria SRB in industrial aqueous systems of chemical production and oil refining. Inhibition of production of biogenic sulphide with SRB takes place as a result of synergetic action of a biocide component in a first concentration and a metabolic inhibitor in a second concentration. The biocide immediately destroys the first portion of SRB. The biocide component is selected from a group comprising aldehydes, amine-type compounds, halogenated compounds, sulphur compounds, salts of quaternary phosphonium and/or combinations thereof. The metabolic inhibitor inhibits growth of a second portion of SRB without its direct destruction. The metabolic inhibitor component is selected from a group comprising nitrite, molybdate, tungstate, selenate, anthraquinone and/or combinations thereof. Contact between the SRB and the biocide and metabolic inhibitor can take place continuously, intermittently or simultaneously.

EFFECT: method ensures efficient inhibition of production of biogenic sulphide with SRB during combined use of components in considerably lower concentrations than if the biocide or metabolic inhibitor was used separately.

25 cl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to 2-(carboxy-n-alkyl)ethyltriphenyl phosphonium bromides of general formula I, having bactericidal and fungicidal activity, heat resistance and surfactant resistance, which can be used in veterinary, medicine and agriculture , where R = n-C10H21 n-C12H25, n-C14H29, n-C16H33, n-C18H37.

EFFECT: obtaining novel biologically active compounds.

1 cl, 6 ex, 1 tbl

FIELD: chemistry.

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

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

5 cl, 12 ex

FIELD: chemistry.

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

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

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

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

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

14 cl, 76 ex, 3 dwg

FIELD: chemistry.

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

EFFECT: obtaining new ionic liquids with improved electrochemical properties.

15 cl, 18 ex, 2 dwg

FIELD: chemistry.

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

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

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

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

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

19 cl, 5 ex

FIELD: chemistry.

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

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

9 ex, 1 tbl

FIELD: chemistry.

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

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

10 cl

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