WO2007006389A1

WO2007006389A1 - Mixture of onium alkyl sulfonates and onium alkyl sulfites

Info

Publication number: WO2007006389A1
Application number: PCT/EP2006/005743
Authority: WO
Inventors: Nikolai Ignatyev (Mykola); Urs Welz-Biermann; Andriy Kucheryna; Helge Willner
Original assignee: Merck Patent Gmbh
Priority date: 2005-07-14
Filing date: 2006-06-14
Publication date: 2007-01-18
Also published as: DE102005032838A1

Abstract

The invention relates to a method for producing mixtures of onium alkyl sulfonates and onium alkyl sulfites by reacting an onium halogenide or onium carboxylate with a symmetrically substituted dialkyl sulfite or with an asymmetrically substituted dialkyl sulfite at temperatures ranging from 50 to 120 °C as well as to mixtures produced using this method.

Description

Mixture of onium alkyl sulfonates and onium alkyl sulfites

The invention relates to a process for the preparation of mixtures of onium alkyl sulfonates and onium alkyl sulfites by reacting an onium halide or carboxylate with a symmetrically substituted one

Dialkyl sulfite or with an unsymmetrically substituted dialkyl sulfite at temperatures of 50 to 12O ⁰ C and mixtures prepared by this method.

A large number of onium salts, for example alkyl sulfates, are ionic liquids. Ionic liquids, through their properties in modern research, are an effective alternative to traditional volatile organic solvents for organic synthesis. The use of ionic liquids as a novel reaction medium could continue to be a practical solution for both solvent emission and reprocessing problems Catalysts (R. Sheldon, Chem. Commun., 2001, pp. 2399-2407). Ionic liquids or liquid salts are ionic species consisting of an organic cation and a generally inorganic anion. They contain no neutral molecules and usually have melting points less than 373 K. However, the melting point may also be higher without restricting the applicability of the salts in all fields of application. Examples of organic cations include tetraalkylammonium, tetraalkylphosphonium, N-

Alkylpyridinium, 1, 3-dialkylimidazolium or trialkylsulfonium. Among a variety of suitable anions are, for example, BF ₄ ^" , PFe ^" , SbF ₆ ^" , NO ₃ ^" , CF ₃ SO ₃ ^" , (CF ₃ SO ₂ J ₂ N ^" , alkylSO ₃ ^' , arylSO ₃ ^" , CF ₃ CO ₂ ^" , CH ₃ CO ₂ ^" or AI ₂ CI ₇ ^" to call.

Ionic liquids with alkyl sulfite or aryl sulfite anions are not known. Only isolated onium salts with methylsulfite anion are in the Literature, eg trimethylphenylammonium methylsulfite (W. Voss and E. Blanke, Justus Liebigs Ann. Chem., 485 (1931), pp. 258-279) or tetrabutylammonium methylsulfite (M. Julia et al., Tetrahedron, 42 (1986), pp. 3841-3850).

It is known that mixtures of two or more components, e.g. Salts, have a lower melting point than the respective individual components. Such mixtures are also referred to as eutectic mixtures. Such mixtures are widely used, e.g. in metallurgy, for example in the production of aluminum. The formation of eutectic mixtures is also conceivable for ionic liquids, but so far has not been used, since so far each individual component must be prepared in separate synthesis steps on different reaction routes. This makes a mix more expensive and thus more impractical than a system based on a single component.

Accordingly, it was an object of the present invention to provide a process for the preparation of mixtures of onium alkyl sulfonates and onium alkyl sulfites, which is to be carried out in a simple manner. Another object was the provision of appropriate mixtures, which can be used inter alia as ionic liquid.

The object is achieved by the method according to the invention. The invention therefore provides a process for preparing mixtures of onium alkyl sulfonates and onium alkyl sulfites by reacting an onium halide or onium carboxylate with a symmetrically substituted dialkyl sulfite or with an unsymmetrically substituted dialkyl sulfite at temperatures of 50 to 120 ^° C. The inventive method has the advantage that no alkyl group of the sulfite used is transferred to the cation and thus the substitution pattern in the cation of the choice of Alkansulfonatanions or Alkylsulfitanions is independent. Moreover, the dialkyl sulfites used are less toxic than alkyl sulfate esters. As by-products of the process according to the invention, alkyl halides or esters are obtained, which in turn can be used as valuable reagents. In addition, the alkyl halides which are by-produced when using onium halides are generally gases or volatile compounds which can be removed from the reaction mixture without great expense in terms of process engineering

The mixture provided by the method according to the invention represents a new type of ionic liquids. The mixture according to the invention can not only be used for a number of fields of application, in particular as an ionic liquid, but can also be used as a reactive ionic liquid the onium alkyl sulfonate acts as an inert solvent and the onium alkyl sulfite, for example, as a reducing reagent or as an antioxidant. The composition of the mixture can be controlled in a simple manner by varying the starting compounds and by adjusting the process parameters.

Of course, the use of both symmetrically substituted dialkyl sulfites having 1 to 10 carbon atoms or the use of unsymmetrically substituted dialkyl sulfites having 1 to 10 carbon atoms or even higher alkylated starting materials in the process according to the invention is possible.

Onium halides suitable for the process according to the invention are ammonium halides, phosphonium halides, thiouronium halides, guanidinium halides or heterocyclic cation halides, where the halides can be selected from the group of chlorides or bromides. Preference is given in the process according to the invention

Ammonium, phosphonium, guanidinium halides or halides with heterocyclic cation used. Onium carboxylates suitable for the process according to the invention are ammonium carboxylates, phosphonium carboxylates, thiouronium carboxylates, guanidinium carboxylates or carboxylates with a heterocyclic cation, where the carboxylates are selected from the group consisting of carbonates, formates, acetates,

Propylates or butylates can be selected. In the process according to the invention, preference is given to using ammonium, phosphonium, guanidinium carboxylates or carboxylates with a heterocyclic cation, in particular ammonium, phosphonium, guanidinium acetates or acetates having a heterocyclic cation.

Onium halides are preferably used in the process according to the invention.

The onium halides or carboxylates are usually commercially available or can be prepared by synthetic methods as known from the literature, e.g. in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart or Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999. One can also make use of known per se, not mentioned here variants.

Ammonium or phosphonium halides can be described, for example, by the formula (1)

[XR ₄ J ⁺ HaI ^" (1), where

XN ₁ p

Hal is Cl or Br and R are each independently

H, where not all substituents R may be H at the same time, straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 C

Atoms, which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more R partially with Cl, Br and / or CN or partially or completely with -F or F and Cl, or F and Br, or F Cl and Br may be substituted, but not all four or three R may be fully substituted with halogens, and one or two non-adjacent and not α- or αz -containing

Carbon atoms of R, by atoms and / or atomic groups selected from the group -O-, -C (O) -, -S-, -S (O) - or -SO ₂ - may be replaced.

Excluded are therefore compounds of the formula (1) in which all four or three substituents R are completely substituted by halogens, for example tris (trifluoromethyl) methylammonium chloride, tetra (trifluoromethyl) ammonium chloride or tetra (nonafluorobutyl) phosphonium chloride.

Guanidinium halides can be described, for example, by the formula (2), [C (NR ¹ R ² ) (NR ³ R ⁴ ) (NR ⁵ R ⁶ )] ⁺ Hal ^' (2), wherein

HaI Cl or Br and

R ¹ to R ^{6 are} each independently

Is hydrogen or CN, straight-chain or branched alkyl having 1 to 20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, wherein a or more of the substituents R ¹ to R ^{6 may be} partially substituted with -NO ₂ , CN, Cl and / or Br, partially or fully substituted with F, or F and Cl, or F and Br or F, Cl and Br, but wherein not all substituents on an N atom may be completely substituted by halogens, wherein the substituents R ¹ to R ⁶ may be linked in pairs by single or double bond and wherein one or two non-adjacent, not directly bonded to the heteroatom and not permanent carbon atoms of the substituents R ¹ to R ^{6 can be} replaced by atoms and / or atomic groups selected from the group -O-, -C (O) -, -S-, -S (O) - or -SO ₂ -.

Thiouronium halides can be exemplified by the formula (3)

[(R ¹ R ² N) -C (= SR ⁷ ) (NR ³ R ⁴ )] ⁺ Hal ^" (3), wherein

HaI Cl or Br and

R ¹ to R ⁴ and R ^{7 are} each independently hydrogen or CN, wherein hydrogen is excluded for R ⁷ , straight-chain or branched alkyl having 1 to 20 C-atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or a plurality of double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 C

Atoms which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more of the substituents R ¹ to R ⁴ and R ⁷ partially or completely with F, Cl and / or Br, in particular -F and / or -Cl, or may be partially substituted with CN, but not all

Substituents may be substituted on an N atom completely with halogens, wherein the substituents R ¹ to R ⁷ and may be connected in pairs by single or double bond and wherein one or two non-adjacent, not directly bonded to the heteroatom and not ω-permanent Carbon atoms of the substituents R ¹ to and R ⁷ by atoms and / or atomic groups selected from the group -O-, -C (O) -, -S-,

-S (O) - or -SO ₂ - can be replaced.

Halides with a heterocyclic cation can be obtained, for example, by the

Formula (4) are described

[HetN] ⁺ Hai ^" (4), where Hal is Cl or Br and

HetN ⁺ a heterocyclic cation selected from the group

Imidazolium 1 H-pyrazolium 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium

4,5-dihydro-lmidazolinium

2,5-dihydro-imidazolinium pyrrolidinium

1, 2,4-triazolium 1, 2,4-triazolium

means, wherein the substituents

R ¹ 'to R ⁴ ' are each independently

Hydrogen or CN, straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,

Dialkylamino with alkyl groups having 1-4 C atoms, which, however, not on

Heteroatom of the heterocycle is present, saturated, partially or completely unsaturated cycloalkyl having 3-7 C

Atoms, which may be substituted by alkyl groups having 1-6 C atoms or aryl-CrC ₆ alkyl, wherein the substituents R ¹ 'and R ⁴ ' partially or completely with F, Cl and / or Br, in particular -F and / or -Cl may be substituted, but not simultaneously R ^{1 '} and R ^{4' are} CN or may be completely substituted with F or other halogens, wherein the substituents R ² and R ^{3 may be} partially or completely substituted by F, Cl and / or Br, in particular -F and / or -Cl, or partially substituted by NO ₂ or CN and wherein one or two non-adjacent, not directly on Heteroatom bound and not

Carbon atoms of the substituents R ¹ 'to R ⁴ ', by atoms and / or atomic groups selected from the group -O-, -C (O) -, -S-, -S (O) - or -SO ₂ - may be replaced ,

The C ₁ -C 20 -alkyl group is, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1, 2 or 3

Methylbutyl, 1, 1, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl. Optionally fluorinated alkyl groups, for example difluoromethyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl.

A straight-chain or branched alkenyl having 2 to 20 C atoms, wherein several double bonds may also be present, is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, iso-pentenyl, Hexenyl, heptenyl, octenyl, -C ₉ Hi ₇ , -CioH ₁₉ to -C ₂₀ H ₃₉ ; preferably vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl.

A straight-chain or branched alkynyl having 2 to 20 C atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore 4-pentynyl, 3-pentynyl, hexynyl, Heptynyl, octynyl, -C ₉ H ₁₅ , -C ₁₀ Hi ₇ to -C ₂₀ H ₃ 7, preferably ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, 4-pentynyl, 3-pentynyl or hexynyl.

In the context of the present invention, completely unsaturated cycloalkyl also means aromatic substituents. Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms are therefore cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclopenta-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 may be substituted by Cr to C ₆ alkyl groups, in turn, the cycloalkyl group or with the Cr to C ₆ - Alkyl-substituted cycloalkyl group may also be substituted by F or F and Cl. However, the cycloalkyl groups may likewise be substituted by further functional groups, for example by CN, SO ₂ R ', SO ₂ OR', SO ₂ NH _2, C (O) NH ₂ or C (O) OR '. R 'has a meaning defined below.

ArylCrC ₆ -alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, where both the phenyl ring and the alkylene chain, as described above, may be partially or completely substituted by -F, or F and Cl, more preferably benzyl or phenylpropyl. However, the phenyl ring or the alkylene chain can likewise be substituted by further functional groups, for example by CN, SO ₂ R ', SO ₂ OR', SO ₂ NH ₂ , C (O) NH ₂ or C (O) OR '.

R 'does not mean partially or perfluorinated C ₁ to C ₆ alkyl, C ₃ to C ₇ cycloalkyl, unsubstituted or substituted phenyl. In R ', C ₃ - to C ₇ - cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

In R 'is phenyl substituted by C ₁ - to C ₆ -alkyl, d- to C ₆ - alkenyl, NO _2, F, Cl, Br, I, -C ₆ alkoxy, SCF _3, SO ₂ CF _3, SO ₂ CH ₃ , COOR ", SO ₂ X ', SO ₂ NR" ₂ or SO ₃ R "substituted phenyl, wherein X' is F, Cl or Br and R" is an unfluorinated or partially fluorinated C ₁ to C ₆ alkyl or C ₃ - to C ₇ - Cycloalkyl as defined for R ', for example, o-, m- or p-methylphenyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o-, m- or p-isopropylphenyl, o-, m- or p-nitrophenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m-, p- (trifluoromethyl) phenyl, o-, m-, p (Trifluoromethoxy) phenyl, o-, m-, p-

(Trifluoromethylsulfonyl) phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodophenyl, more preferably 2.3 , 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-difluorophenyl, 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- Dimethoxyphenyl, 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl or 2,4,5-trimethylphenyl.

In the substituents R, R ¹ to R ⁷ or R ^{1 '} to R ⁴ also one or two non-adjacent, not directly bonded to the heteroatom and not ω-standing carbon atoms, by atoms and / or atomic groups selected from the group -O- , -C (O) -S-, -S (O) - or -SO ₂ - be replaced.

Without restricting generality, examples of such modified substituents R, R ¹ to R ⁷ and R ^{1 '} to R ^{4' are} :

-OCH ₃ , -OCH (CHs) ₂ , -CH ₂ OCH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -C ₂ H ₄ OCH (CH ₂ ) ₂ , -C ₂ H ₄ SC ₂ H ₅ , -C ₂ H ₄ SCH (CHs) ₂ , -S (O) CH ₃ , -SO ₂ CH ₃ , -SO ₂ C ₆ H ₅ , -SO ₂ C ₃ H ₇ , -SO ₂ CH (CHa) ₂ , -SO ₂ CH ₂ CF ₃₁ -CH ₂ SO ₂ CH ₃ , -O-C ₄ H ₈ -OC ₄ H ₉ , -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CF ₂ CF ₂ H, -CF ₂ CHFCF ₃ , -CF ₂ CH (CFs) ₂ , -C ₂ F ₄ N (C ₂ F ₅ ) C ₂ F ₅ , -CHF ₂ , -CH ₂ CF ₃ , - C ₂ F ₂ H ₃ , -C ₃ FH ₆ , -CH ₂ C ₃ F ₇ , -CH ₂ C (O) OCH ₃ , -CH ₂ C (O) CH ₃ , -CH ₂ C ₆ H ₅ or - C (O) C ₆ H ₅ .

The substituents R ¹ to R ⁷ are each, independently of one another, preferably a straight-chain or branched alkyl group having 1 to 10 C atoms. The substituents R ¹ and R ² , R ³ and R ⁴ and R ⁵ and R ⁶ in compounds of the formulas (2) and (3) may be the same or different. More preferably, R ¹ to R ^{7 are} each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, phenyl or cyclohexyl, most preferably methyl, ethyl, n-propyl, isopropyl or n-butyl , However, the substituents R and R ¹ to R ⁷ may also be substituted by further functional groups, for example by

CN, SO ₂ R ', SO ₂ OR ", SO ₂ NH ₂ , SO ₂ NR' _2l C (O) NH ₂ , C (O) NR ' ₂ or C (O) OR'. R 'has one previously defined meaning.

As the substituents R ¹ to R ⁴ of compounds of the formula (4) are according to the invention, besides hydrogen, preferably: CN, d- to C ₂₀ -, in particular Cr to C ₂ alkyl groups, and saturated or unsaturated, ie also aromatic, C ₃ - to C ₇ -cycloalkyl groups which may be substituted by Cr to Cβ-alkyl groups, in particular phenyl or aryl-Ci-C ₆ -alkyl.

The substituents R ¹ and R ⁴ are each, in each case independently of one another, more preferably CN, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, pentyl, hexyl, octyl, decyl, cyclohexyl, phenyl, phenylpropyl or benzyl. They are very particularly preferably methyl, CN, ethyl, n-butyl or hexyl. In pyrrolidinium or piperidinium compounds, the two substituents R ¹ and R ^{4 are} preferably different.

The substituent R ² or R ³ is, in each case independently of one another, in particular hydrogen, dimethylamino, diethylamino, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl, cyclohexyl, phenyl or benzyl.

R ² is particularly preferably hydrogen, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or dimethylamino. Most preferably, R ² and R ^{3 'are} hydrogen.

In one embodiment, the alkyl groups as substituents R and R ¹ to R ⁶ and R ¹ and R ^{4 of} the heterocyclic cations of formula (4) are different from the alkyl group of the anion in onium alkyl sulfite. However, the onium alkyl sulfite prepared according to the invention may also have alkyl groups in the cation which are the same as the alkyl group in the anion, but which have not been introduced by alkylation according to the invention.

Up to four substituents of the guanidinium cation

[C (NR ¹ R ² ) (NR ³ R ⁴ ) (NR ⁵ R ⁶ )] ⁺ can also be linked in pairs in such a way that mono-, bi- or polycyclic cations are formed.

Without limitation of generality are examples of such

Guanidinium cations are:

, the

Substituents R ¹ to R ³ and R ^{6 may have} a meaning given above or particularly preferred.

If desired, the carbocyclic or heterocyclic rings of the above-mentioned guanidinium cations or by d- to C ₆ alkyl, Cr and Ce-alkenyl, NO _2, F, Cl, Br, I, C ₁ -C ₆ -alkoxy, SCF _3, SO ₂ CF ₃ , SO ₂ CH ₃ , CN, COOR ", SO ₂ NR" ₂ , SO ₂ X 'or SO ₃ R ", where X ^{1 is} F, Cl or 5 Br and R" is an unsubstituted or partially fluorinated C ₁ to C ₆ alkyl or C ₃ to C ₇ cycloalkyl as defined for R 'or substituted by substituted or unsubstituted phenyl.

Up to four substituents of the thiouronium cation [(R ¹ R ² N) - O C (= SR ⁷ ) (NR ³ R ⁴ )] ⁺ may also be linked in pairs in such a way that mono-, bi- or polycyclic cations are formed. Without restriction of generality, examples of such cations are given below:

where Y = S and the

Substituents R ¹ , R ³ and R ^{7 may have} a previously given or particularly preferred meaning.

Optionally, the carbocycles or heterocycles of the above-mentioned thiouronium cations can still by Cr to Cβ-alkyl, Ci to Ce alkenyl, NO ₂ , F, Cl, Br, I ₁ Ci-C ₆ alkoxy, SCF ₃ , SO ₂ CF ₃ , SO ₂ CH ₃ , COOR ", SO ₂ NR" ₂ , SO ₂ X 'or SO ₃ R ", where X' is F, Cl or Br and R" is a non, partially or perfluorinated C _r to C ₆ -alkyl or C ₃ - to C ₇ -cycloalkyl as defined for R 'or substituted by substituted or unsubstituiert.es phenyl.

However, the substituents R ¹ to R ⁴ may likewise be substituted by further functional groups, for example by CN, SO ₂ R ',

SO ₂ OR 'or COOR'. R 'has a previously defined meaning.

HetN ^{+ of} the formula (4) is preferable Pyridinium Pyrimidinium

Imidazolium pyrazolium pyrrolidinium

wherein the substituents R 1 ¹ 'ub: is "o R4 ⁴ ' each independently of one another have a meaning as described above.

HetN ⁺ is particularly preferably imidazolium, pyrrolidinium or pyridinium, as defined above, wherein the substituents R ^{1 '} to R ^4' each independently have a meaning as described above.

In the abovementioned formulas (1) to (4), Hal can be replaced by carboxylates according to the invention, as defined above. The choice of anion does not limit the choice of cation.

The symmetrically substituted dialkyl sulfite used in the process according to the invention is preferably a dialkyl sulfite having a straight-chain or branched alkyl group having 1-10 C atoms, preferably having 1-4 C atoms, particularly preferably having 1-2 C atoms. The alkyl group is preferably a straight-chain or branched alkyl group having 1-4 C atoms, such as, for example, methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl. Preferably, the alkyl group is methyl or ethyl.

Examples of symmetrically substituted dialkyl sulfites are dimethyl sulfite, diethyl sulfite, di- (n-propyl) sulfite, di- (iso-propyl) sulfite, di- (n-butyl) sulfite or Di- (sec-butyl) sulfite. Preference is given to using dimethyl sulfite or diethyl sulfite.

The symmetrical dialkyl sulfites used are usually commercially available or can be prepared by synthetic methods as known from the literature, e.g. in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart or Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999, or from the article by W. Voss and E. Blanke, Justus Liebigs Ann. Chem., 485 (1931), pp. 258-279. One can also make use of known per se, not mentioned here variants.

As unsymmetrically substituted dialkyl sulfite is preferably a dialkyl sulfite having a straight-chain or branched alkyl group having 1 to 10 carbon atoms and a methyl or ethyl group as the second alkyl group, preferably having an alkyl group having 3-8 carbon atoms used. Examples of asymmetrically substituted dialkyl sulfites are methyl propyl sulfite, methyl butyl sulfite, ethyl butyl sulfite, methyl pentyl sulfite, ethyl pentyl sulfite, methyl hexyl sulfite, ethyl hexyl sulfite, methyl heptyl sulfite, ethyl heptyl sulfite, methyl octyl sulfite or ethyl octyl sulfite.

The unsymmetrical dialkyl sulfites used can be prepared by synthesis processes as described in the literature, for example in the standard works such as Houben-Weyl, Methods of Organic Chemistry, Georg-Thieme-Verlag, Stuttgart or Richard C. Larock, Comprehensive Organic Transformations, 2nd Edition, Wiley-VCH, New York, 1999, or from the article by W. Voss and E. Blanke, Justus Liebigs Ann. Chem., 485 (1931), pp. 258-279, or VM Pavlov, J. Gen. Chem. Chem. USSR (Eng. Transl.), 41 (1971), pp. 2559-2561. One can also make use of known per se, not mentioned here variants. A general scheme summarizes the process according to the invention, wherein the arrow in the resulting alkyl halogen compound is a symbol for the volatility of the compound:

[XRJ ⁺ Hal (1) or [C (NR ¹ R ² ) (NR ³ R ⁴ ) (NR ⁵ R ⁶ )] ⁺ Hal (2) or X = N ₁ P

[(R ¹ R ² N) -C (= YR ⁷ ) (NR ³ R ⁴ )] ⁺ Hal ( ₃ ) _{o of} the [HetN] ⁺ Hah (4)

+ [(Alkyl-O) ₂ SO]

[XRJ ^ alkyl-SOJ / [XR ₄ ] ⁺ [alkyl-O-SO ₂ ] - (5) or X = N ₁ P

[C (NR ¹ R ²⁾ (NR ³ R ⁴⁾ (NR5R6)] ⁺ [alkyl-SO _3] - / [C (NR ¹ R ²⁾ (NR ³ R ⁴⁾ (NR ⁵ R ^6)] ⁺ [ Alkyl-O-SO ₂ ] - (6) or [(R ¹ R ² N) -C (= YR ⁷ ) (NR ³ R ⁴ )] ⁺ [alkyl-SO ₃ ] / [(R ¹ R ² N) -C (= YR ⁷ ) (NR ³ R ⁴ )] ⁺ [alkyl-O-SO ₂ ] - (7) or [HetN] ⁺ [alkyl-SO ₃ ] / [HetN] ⁺ [alkyl-O-SO ₂ ] - (8) + alkyl-Hal |

The substituents R, R ¹ to R ⁷ and HetN ^{+ of} the mixtures of the formulas (1) to (8) correspond to the meanings as described above.

The reaction with dialkyl sulfites is carried out at temperatures between 50 and 120 ⁰ C, preferably at temperatures between 70 and 100 ° C. The choice of the optimum reaction temperature depends on the amount of excess of the dialkyl sulfite and on the nature of the halide and the dialkyl sulfite used.

No solvent is needed. However, it is also possible to use solvents, for example dimethoxyethane, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, propionitrile, dichloromethane or mixtures with one another. The reaction is carried out with an excess or equimolar amount of dialkyl sulfite, preferably with a slight excess of dialkyl sulfite.

Likewise provided by the present invention are mixtures of

Onium alkyl sulfonates and onium alkyl sulfites of the formula (9) obtainable by the process according to the invention:

[Kt] ⁺ [alkyl-SO ₃ ] - / [Kt] ⁺ [alkyl-O-SO ₂ ] ^" (9) where K t represents tetraalkylammonium, phosphonium, guanidinium, thiouronium cations or heterocyclic cations By the use of the method according to the invention, access to these mixtures is simplified and thus the possibility of using these mixtures is increased.

It will be understood by those skilled in the art that all of the aforementioned substituents, such as H, N, O, Cl, F, may be replaced by the corresponding isotopes.

The use of the mixtures of the formula (9) according to the invention as a solvent, solvent additive, heat transfer, reducing agent, antioxidant, phase transfer catalyst, as extractant, as an additive, as a surfactant, as an electrolyte in galvanic cells, as a modifier or as a plasticizer is also the subject of present invention.

The mixtures of formula (9) are also suitable as starting material for the synthesis of mixtures of onium salts with alkyl sulfonate and alkyl sulfate anions by oxidation. Suitable oxidizing agents in this reaction are all oxidizing agents known to those skilled in the art, for example oxygen. In the case of use as a solvent or solvent additive, the mixtures according to the invention in any known to those skilled in the type of reaction, for example, transition metal, enzyme, or with other biocatalysts catalyzed reactions, such as

Hydroformylation reactions, oligomerization reactions, C-C bond-linking reactions, e.g. the Heck coupling, but also esterifications, isomerization reactions or reactions for Amidbindungsknüpfung.

Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent. The preferred embodiments and examples are therefore to be considered as merely illustrative, in no way limiting as in any way limiting disclosure.

The NMR spectra were measured on solutions in deuterated solvents at 20 ^° C. on a Bruker ARX 400 spectrometer with a 5 mm ¹ H / BB broadband head with deuterium lock, unless indicated in the examples. The measurement frequencies of the different cores are: ¹ H: 400.13 MHz and ³¹ P .161.98 MHz. The referencing method is specified separately for each spectrum or for each data record.

Examples:

Example 1: Mixture of 1-butyl-3-methylimidazoliummethylsulfite and 1-butyl-3-methylimidazolium methanesulfonate

C ₄ Hg-NVy N-CH ₃ +

Cl- CH ₃ OSOa CH ₃ SO ₃ - A mixture of 9.96 g (57.0 mmol) of i-butyl-3-methylimidazoliumchlorid and 6.29 g (57.1 mmol) of dimethyl sulfite is stirred at 60-70 ⁰ C (temperature of the oil bath) for 24 hours under inert gas atmosphere (nitrogen) in a closed 100 ml reaction vessel , The end of the reaction is determined by NMR measurement. The product is vacuumed at 13.3

Pa and 70 ⁰ C (temperature of the oil bath) pumped within 2 hours. This gives 13.33 g of a liquid mixture of 1-butyl-3-methylimidazoliummethylsulfit and 1-butyl-3-methylimidazoliummethylsulfonat in a molar ratio of about 1: 3. The yield is almost quantitative. The product is analyzed by NMR spectroscopy.

¹ H NMR (reference: TMS; solvent: CD ₃ CN), ppm: 0.90 1 (CH ₃ ); 1.29 m (CH ₂ ); 1.80 m (CH ₂ ); 2.46 s (CH ₃ SO ₃ ); 3.20 s (CH ₃ OSO _2); 3.87 s (CH ₃ ); 4.18 1 (CH ₂ ); 7.50 m (CH); 7.52 m (CH); 9.34 br. s. (CH); ³ J _{H | H} = 7.1 Hz.

Example 2: Mixture of 1-butyl-3-methylimidazoliumethylsulfite and 1-butyl-3-methylimidazoliumethanesulfonate

C ₄ Hj-NV y. N-CH ₃ + (C ₂ H ₅ O) ₂ SO - ^ - S. C ₄ H ₉ -NV) N-CH ₃ + C ₄ H ₉ -Nv) N-CH ₃ + C ₂ H ₅ Cl I ^{ci ~} C ₂ H ₅ OSO ₂ - C ₂ H ₅ SO ₃ -

A mixture of 3:51 g (20.1 mmol) of 1-butyl-3-methylimidazolium chloride and 3:06 g (22.1 mmol) diethyl sulfite is at 120 ⁰ C (temperature of oil bath) for 19 hours under an inert atmosphere (nitrogen) in a closed reaction vessel equipped with a pressure valve for 1- 1.5 bar overpressure stirred. The end of the reaction is determined by NMR measurement. The product is pumped off in vacuo at 13.3 Pa and 100 ° C (temperature of the oil bath) within 1 hour. This gives 4.75 g of a liquid mixture of 1-butyl-3-methylimidazoliumethylsulfit and 1-butyl-3-methylimidazoliumethylsulfonat in a molar ratio of about 1: 2. The yield is 95.2%. The product is analyzed by NMR spectroscopy. ¹ H NMR (reference: TMS; solvent: CD ₃ CN), ppm: 0.91 t (CH ₃ ); 1.08 t (CH ₃ ); 1.15 t (CH ₃ ); 1.30 m (CH ₂ ); 1.80 m (CH ₂ ); 2.53 q (CH ₂ SO ₃ ); 3.52 q (CH ₂ OSO ₂ ); 3.86 s (CH ₃ ); 4.17 1 (CH ₂ ); 7.43 m (CH); 7.45 m (CH); 9.20 br. s. (CH); ³ JH ₁ H = 7.1 Hz; ³ J _H , H = 7.4 Hz.

Example 3: Mixture of 1-hexyl-3-methylimidazoliumethylsulfite and 1-hexyl-3-methylimidazoliumethanesulfonate

C ₆ H _ir OO N-CH _{3 +} C ₂ H ₅ ClI

A mixture of 10.58 g (52.2 mmol) of 1-hexyl-3-methylimidazolium- chloride and 7.58 g (54.9 mmol) Diethylsulfit is at 120 ⁰ C (temperature of the oil bath) for 19 hours under inert gas atmosphere (nitrogen) in a closed reaction vessel with pressure valve for Stirred at 1-1.5 bar overpressure. The end of the reaction is determined by NMR measurement. The product is pumped off in vacuo at 13.3 Pa and 100 ⁰ C (temperature of the oil bath) within 1 hour. This gives 13.61 g of a liquid mixture of 1-hexyl-3-methylimidazoliumethylsulfit and 1-hexyl-3-methylimidazoliumethylsulfonat in a molar ratio of about 1: 3. The yield is 94.3%. The product is analyzed by NMR spectroscopy.

¹ H NMR (reference: TMS; solvent: CD ₃ CN), ppm: 0.86 t (CH ₃ ); 1.08 1 (CH ₃ ); 1.15 1 (CH ₃ ); 1.28 m (3CH ₂ ); 1.81 m (CH ₂ ); 2.53 q (CH ₂ SO ₃ ); 3.51 q (CH ₂ OSO ₂ ); 3.85 s (CH ₃ ); 4.151 (CH ₂ ); 7.42 d, d (CH); 7.45 d, d (CH); 9.12 br. s. (CH); ³ J _H , H = 7.1 Hz; ³ J _H , H = 7.4 Hz; ⁴ J _H , H = 1.5 Hz.

Example 4: Mixture of tetrabutylammonium methylsulfite and

tetrabutylammonium methanesulfonate 120 ° C

[(C ₄ Hg) ₄ N] ⁺ CH ₃ C (O) O- (CH ₃ O) ₂ SO [(C ₄ Hg) ₄ N] ⁺ CH ₃ OSO ₂ - + iy π

⁺ [(C ₄ Hg) ₄ N] ⁺ CH ₃ SO ₃ - + CH ₃ C (O) OCH ₃ A mixture of 3.01 g (10.0 mmol) of tetrabutylammonium acetate and

1.11 g (10.1 mmol) of dimethyl sulfite is stirred at 120 (temperature of the oil bath) for 19 hours under an inert gas atmosphere (nitrogen) in a closed 50 ml reaction vessel. The end of the reaction is determined by NMR measurement. The product is pumped off in vacuo at 13.3 Pa and 6O ⁰ C (temperature of the oil bath) within 1 hour. This gives 3.34 g of a liquid mixture of tetrabutylammonium methylsulfite and tetrabutylammonium methanesulfonate. The yield is almost quantitative. The product is analyzed by NMR spectroscopy.

¹ H NMR (reference: TMS; solvent: CD ₃ CN), ppm: 0.95 1 (CH ₃ ); 1.34 t, q (CH ₂ ); 1.60 m (CH ₂ ); 2.42 s (CH ₃ ); 3.11 m (CH ₂ ); 3.16 s (CH ₃ O); ³ J _H, H =

7.3 Hz.

Claims

claims

1. A process for the preparation of mixtures of onium alkyl sulfonates and onium alkyl sulfites by reacting an onium halide or carboxylate with a symmetrically substituted dialkyl sulfite or with an unsymmetrically substituted dialkyl sulfite at temperatures of 50 to 12O ⁰ C.

2. The method according to claim 1, characterized in that the reaction with a symmetrically substituted dialkyl sulfite, wherein the

Alkyl group can have 1 to 10 carbon atoms, takes place.

3. The method according to claim 1, characterized in that the reaction with an unsymmetrically substituted dialkyl sulfide, wherein one alkyl group may have 1 to 10 carbon atoms and the second

Alkyl group methyl or ethyl, takes place.

4. The method according to one or more of claims 1 to 3, characterized in that the halide is an ammonium halide, phosphonium halide, Thiouroniumhalogenid, guanidinium halide or halide with heterocyclic cation, wherein the halides can be selected from the group of chlorides or bromides.

5. The method according to one or more of claims 1 to 4, characterized in that the carboxylate is an ammonium acetate,

Phosphonium acetate, a guanidinium acetate or an acetate having a heterocyclic cation.

6. The method according to one or more of claims 1 to 4, characterized in that the halide of the formula (1),

[XFU] ⁺ Hai ^' (1), where XN ₁ p

HaI Cl or Br and

R each independently

Atoms, which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more R partially with Cl, Br and / or CN or partially or completely with -F or F and Cl, or F and Br, or F Cl and Br may be substituted, but not all four or three R may be fully substituted with halogens, and one or two non-adjacent and non-α or ω-permanent

7. The method according to one or more of claims 1 to 4, characterized in that the halide of the formula (2) corresponds to, [C (NR ¹ R ² ) (NR ³ R ⁴ ) (NR ⁵ R ⁶ )] ⁺ HaP ( 2), where

HaI Cl or Br and

R ¹ to R ^{6 are} each independently

Is hydrogen or CN, straight-chain or branched alkyl having 1 to 20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, wherein a or more of the substituents R ¹ to R ^{6 may be} partially substituted with -NO ₂ , CN, Cl and / or Br, partially or fully substituted with F, or F and Cl, or F and Br or F, Cl and Br, but wherein not all substituents on an N atom may be completely substituted by halogens, wherein the substituents R ¹ to R ⁶ may be linked in pairs by single or double bond and wherein one or two non-adjacent, not directly bonded to the heteroatom and not permanent carbon atoms of the substituents R ¹ to R ⁶ by atoms and / or atomic groups selected from among

Group -O-, -C (O) -, -S-, -S (O) - or -SO ₂ - may be replaced.

8. The method according to one or more of claims 1 to 4, characterized in that the halide of the formula (3), [(R ¹ R ² N) -C (= SR ⁷ ) (NR ³ R ⁴ J] ⁺ Hal are described in ^"(3), wherein

HaI Cl or Br and

R ¹ to R ⁴ and R ^{7 are} each independently of one another hydrogen or CN, wherein hydrogen is excluded for R ⁷ , straight-chain or branched alkyl having 1 to 20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more Double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds, saturated, partially or completely unsaturated cycloalkyl having 3-7 C

Atoms which may be substituted by alkyl groups having 1-6 C atoms, wherein one or more of the substituents R ¹ to R ⁴ and R ⁷ partially or completely with F, Cl and / or Br, in particular -F and / or -Cl, or may be partially substituted by CN, but not all substituents on an N atom may be completely substituted with halogens, wherein the substituents R ¹ to R ⁷ and may be connected in pairs by single or double bond and wherein a or two non-adjacent carbon atoms of the substituents R ¹ to and R ^{7 which are} not bonded directly to the heteroatom and are not αz-bonded by atoms and / or atomic groups selected from the group -O-, -C (O) -, -S-, - S (O) - or -SO ₂ - can be replaced.

9. The method according to one or more of claims 1 to 4, characterized in that the halide of the formula (4),

[HetN] ⁺ Har (4), where Hal is Cl or Br and

HetN ⁺ a heterocyclic cation selected from the group

Imidazolium 1H-pyrazolium 3H-pyrazolium 4H-pyrazolium 1-pyrazolinium

2-pyrazolinium 3-pyrazolinium 2,3-dihydro-imidazoliniurono 4,5-dihydro-imidazolinium

2,5-dihydro-imidazolinium pyrrolidinium., _{| 2i} 4_ _{triazo |} 1, 2,4-triazolium

piperidinium

Mor holinium pyrazinium thiazolium oxazolium

means, wherein the substituents

R ¹ 'to R ⁴ ' are each independently

Is hydrogen or CN ₁ straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,

Dialkylamino having alkyl groups with 1-4 C atoms, which is not bound to the heteroatom of the heterocycle, saturated, partially or fully unsaturated cycloalkyl having 3-7 C-

Atoms which may be substituted by alkyl groups having 1-6 C atoms or aryl-C ₁ -C ₆ -alkyl, where the substituents R ¹ 'and R ⁴ ' are partially or completely substituted by F, Cl and / or Br, in particular F and / or -Cl may be substituted, but not simultaneously R ¹ and R ^{4 are} CN or may be fully substituted with F or other halogens, wherein the substituents R ^{2 '} and R ^{3 may be} partially or completely substituted with F, Cl and / or Br, in particular -F and / or -Cl, or partially with NO ₂ or CN and wherein one or two non-adjacent, not directly carbon atoms of the substituents R ¹ 'to R ⁴ ' bonded to the heteroatom and not at random, by atoms and / or atom groups selected from the group -O-, -C (O) -, -S-, -S (O) - or -SO ₂ - can be replaced.

10. The method according to one or more of claims 1 to 9, characterized in that the reaction of the halide with the

Dialkyl sulfite is carried out without solvent.

11. Mixtures of onium alkyl sulfonates and onium alkyl sulfites of the formula (9) obtainable by the process according to claim 1 [Kt] ⁺ [Al kVl-SO ₃ ] ^'' / [Kt] ⁺ [Al kVl-O-SO ₂ ] ^' ( 9) where Kt is tetraalkylammonium, phosphonium, guanidinium,

Thiouronium cations or heterocyclic cations means.

12. Use of mixtures according to claim 11 as solvent, solvent additive, heat transfer medium, reducing agent,

Antioxidant, phase transfer catalyst, as an extractant, as an additive, as a surfactant, as an electrolyte in galvanic cells, as a modifier or as a plasticizer.